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The photocatalysts used were titanium peroxide and Degussa p25 TiO2 pretreated with H2O2. These photocatalysts were investigated by SEM and FTIR spectroscopy. <span style="">&nbsp / </span><o:p></o:p></span></p> <span style="font-size: 12pt / font-family: &quot / Times New Roman&quot / ,&quot / serif&quot / "><o:p></o:p></span></p> </p>

Upwelling, atmospheric nitrogen (N2) fixation by cyanobacteria, and freshwater inputs from the Mississippi River system have been shown to stimulate new production by alleviating nitrogen (N) limitation in the northern Gulf of Mexico (GoM). Stable carbon (delta13C) and nitrogen (delta15N) isotopes were used to investigate whether these sources are utilized differentially by coastal and marine pelagic food webs. Particulate organic matter (POM), Trichodesmium, and zooplankton were collected from the Mississippi River plume and Loop Current (LC) which were detected using remote sensing data. Stable isotope values were used to separate coastal and marine water masses and environmental data (salinity, nutrient and pigment concentrations) allowed me to relate variability to the degree of freshwater influence. Published food web data from these two environments were then assessed to establish whether isotopic baseline shifts observed in our data occur at an ecosystem level. Isotope values of the POM and zooplankton were found to be significantly different between coastal and marine water masses. This was not the case for Trichodesmium whose isotope values were not significantly different between the two water masses. We found that marine water masses (sal > 35) exhibited silicate concentrations, cyanobacterial pigments and DIN: P that suggest an increased abundance of diazotrophs. In contrast, coastal water masses (sal < 35) exhibited increased diatom pigments and molar C:N indicating terrestrial sources fuel phytoplankton production. When published food web data were compared, we found producer and consumer delta15N values were enriched in the coastal compared to the marine environments. This work suggests that differences in delta15N values within my data set and published data reflect a shift in the use of biologically available N where higher trophic levels are sustained by diazotrophic activity in marine environments versus those supported by terrestrial sources in coastal ones. Food webs that have been constructed without considering Trichodesmium as a significant source of organic matter in the GoM should be reconsidered. By re-evaluating published data, this research gives insight into the early life ecology of larval fishes and works to help answer questions about the structure and function of pelagic food webs.

While bacterioplankton indisputably control vital biogeochemical paths in the cycling of carbon and nutrients in the world’s oceans, our knowledge about the functional and genetic diversity of bacterioplankton communities is negligible. In this thesis, molecular and more traditional microbiological methods were used to study the specific function of N2-fixation and in a general sense diversity of marine bacterioplankton species. Most oceans are nitrogen limited and, therefore, adaptive to bacterioplankton capable of N2-fixation. Recent studies have found nifH genes (coding for the nitrogenase enzyme) related to diverse heterotrophic bacteria in oceanic seawater samples indicating that, along with cyanobacteria, also heterotrophic bacteria benefit from N2-fixation. Here, molecular and cultivation methods were used to examine diazotrophic bacterioplankton in the Baltic Sea. We successfully isolated heterotrophic N2-fixing bacteria belonging to the γ-proteobacterial class by means of low-nitrogen plates and semi-solid diazotrophic medium tubes. The isolates required low-O2 conditions for N2-fixation. Using Real-time PCR it was found that heterotrophic bacterioplankton carrying the nifH gene was abundant (3 x 104 nifH gene copies L seawater-1) at locations in the Southwest Baltic proper. With the aim to identify the main N2-fixing organisms in Baltic Proper surface waters, a clone library of nifH gene transcripts (RNA) was generated. Clone inserts were exclusively related to Aphanizomenon sp. and Nodularia sp. Using quantitative real-time PCR it was found that the nifH gene expression from Nodularia sp. was highly variable between stations in the Baltic Proper but was 10-fold higher during mid summer relative to early summer and fall. A diel study showed a 4-fold increase in Nodularia transcript concentrations at early to mid day relative to rest of the day. Real-time PCR was found to be a powerful and highly sensitive method for measuring gene expression. Since nucleic acids are a prerequisite for molecular analyses of bacterioplankton dynamics a protocol to extract DNA from seawater samples was developed with the aim to maximize the yield of high-quality DNA. Each step in the protocol was important for the efficiency of extraction. The obtained extraction efficiencies were up to 92% for seawater samples and up to 96% for isolates. The protocol provides a guideline for DNA extraction from seawater samples for other studies. In a global sampling campaign (9 locations from polar, tropical and temperate regions) we sampled DNA from surface water and constructed 16S rRNA gene libraries to investigate diversity and biogeography of bacterioplankton. Approx. 80% of the sequences found were similar to sequences already deposited in GenBank, indicating that a large fraction of the marine bacterioplankton already has been sampled, which in turn suggests a limited global bacterioplankton diversity. This thesis have improved our knowledge about the composition and nifH gene expression of the diazotrophic bacterioplankton community in the Baltic Sea and contribute significantly to the discussion on global marine bacterioplankton diversity and biogeography. / Östersjön är ett av världens största brackvattensystem. Den ekologiska balansen i detta hav är hotad på grund av övergödning. Mycket arbete har därför fokuserats på att reducera utsläppen av näringsämnen, speciellt kväve. Dessa ansträngningar kan dock motverkas av bakterier som har förmåga att omvandla luftens kväve till metaboliskt användbart ammonium (kvävefixering). På sommaren är Östersjöns primärproduktion begränsad av kväve, med följden att det årligen uppstår massiva blomningar av kvävefixerande bakterier, framför allt cyanobakterier. Dessa är främst Aphanizomenon och Nodularia, men inte endast de fototrofa cyanobakterierna har förutsättningar att fixera N2. NifH gener (genen som kodar för nitrogenas) bärs också av heterotrofa bakterioplankton, vilket har visats i studier i främst Atlanten och Stilla havet. Med hjälp av två olika odlingsmetoder lyckades vi isolera heterotrofa kvävefixerande bakterier tillhörande klassen γ-proteobakteria från Östersjön. Svårigheten med att finna dessa bakterier ligger i att de kräver en miljö med mycket låg syrehalt för att kunna fixera kväve. Resultaten från denna studie ledde oss vidare till att undersöka vilka organismer som uttrycker nifH genen (och då troligen även fixerar kväve) i Östersjön. En av de bakterier som isolerats kunde påvisas med Realtids PCR i ett relativt stort antal (3 x 104 nifH genkopior per liter) vid en av de ursprungliga provtagningsstationerna. För att söka rätt på de olika organismtyper som uttrycker nifH skapades ett klonbibliotek baserat på mRNA extraherat från havsvatten. Det visade sig då att alla de närmare 100 kloner som sekvenserades tillhörde antingen Aphanizominon eller Nodularia. De heterotrofa bakteriernas nifH genuttryck var troligen i jämförelse med dessa cyanobakterier alltför lågt för att kunna detekteras. Realtids PCR mätningar av Nodularias nifH genuttryck visade på en stor variation mellan de olika provtagningsstationerna samt mellan de olika provtagningstillfällena. Vi fann dock en kraftig ökning under juli med en nedgång igen i augusti. En dygnscykelstudie visade att Nodularia nifH genuttrycket ökade under förmiddagen med en topp mitt på dagen för att sedan minska igen. Detta troligen med anledning av att den energikrävande kvävefixeringsprocessen sker under de ljusa timmarna då cellen får energi från fotosyntesen. I de molekylärbiologiska metoderna som används för att få information om identitet och aktivitet hos skilda organismer krävs att DNA och RNA kan extraheras från prover tagna i naturliga vattenmiljöer. Även om antalet bakterier tillsynes är högt, så är mängden DNA och RNA per liter havsvatten relativt låg, därför krävs ett väl fungerande protokoll för denna extraktion. I en inledande studie i denna avhandling optimerades en metod för att utvinna DNA. Ett antal sådana protokoll finns publicerade men dessa har ofta lågt utbyte. Det nya protokollet har hög effektivitet, vilket gör att små provvolymer kan användas (2 ml jämfört med tidigare flera liter) och därmed ökar hanterbarheten. Vi visar i denna studie att varje steg 7 i DNA-extraktionsprotokollet är viktigt för att ge en hög effektivitet. Detta protokoll kan med fördel användas som vägledning för många olika typer av studier. På grund av att många havsbakterier inte kan bilda kolonier och alltså inte växa på traditionella medier har det varit svårt att få en klar bild av artrikedomen. Molekylärbiologin har dock gjort det möjligt att identifiera bakterier med hjälp av 16S rRNA genen, en enorm mängd gensekvenser från världens alla hav har inkommit till den gemensamma databanken (GenBank). År 2002 gjordes en studie där man sammanställde informationen i denna databank, för att få en bild av artrikedomen i världshaven. Resultatet av denna studie var att det i världshaven fanns färre bakterietyper än vad många forskare har spekulerat i. I denna avhandlig har vi utfört en studie där vi gjorde en stor global provtagning för att se om denna undersökning överensstämde med den datainformativa. Provtagning från nio lokaliteter gjordes i de tempererade, tropiska och polarhaven. Ett genbibliotek från varje lokal gjordes och kloner sekvenserades. Resultatet visar i likhet med den datainformativa undersökningen på en begränsad artrikedom. 80% av gensekvenserna fanns redan i databanken, vilket tyder på att de flesta arter redan har blivit funna. Dessutom visade det sig att få av bakterierna återfanns på alla ställen och många återfanns endast på ett ställe. Utöver detta visade det sig att det fanns en ökad artrikedom ju närmare ekvatorn man kom, vilket tidigare har visats för större organismer. Studierna i denna avhandling har ökat förståelsen för hur sammansättningen av det kvävefixerande bakteriesamhället i Östersjön ser ut samt bidragit till diskussionen om den globala artrikedomen bland bakterioplakton och dess utbredning.

The usefulness of preplant nitrogen (N) in establishing alfalfa in colder production areas has not been well characterized. This study was conducted to determine the effect of preplant N and soil temperature on yield, percent N derived from biological nitrogen fixation (PBNF), and shoot N concentration in alfalfa (Medicago sativa L. cv. 'Vernema'. Field experiments were conducted in 1987 and 1988 at Powell Butte, OR, to determine the effect of five levels of preplant N (0, 10, 20, 40, 60 kg ha⁻¹) on yield and shoot N concentration of alfalfa. Growth chamber experiments were conducted from 1989 through 1991 to examine the effect of five levels of preplant N (0, 10, 20, 40, 80 kg ha⁻¹) and three day/ - night soil temperatures (18/12°C, 24/16°C, 27/21°C) on yield, PBNF, and shoot N concentration of alfalfa. In field experiments, preplant N had no effect on shoot N concentration in either year. In 1987 there was no effect of preplant N on dry matter yield. Application of 20-40 kg N ha⁻¹ preplant N increased dry matter yield in 1988. In growth chamber experiments, the highest rate of dry matter accumulation occurred at a soil temperature of 24/16°C. At 18/12°C and 24/16°C, 40 kg ha⁻¹ preplant N resulted in increased shoot and root dry matter yield. At 18/12°C, 80 kg ha-¹ preplant N increased PBNF 14% relative to the zero N control. There was no effect of preplant N on PBNF in plants grown at 24/16°C and 27/- 21°C. The rates of shoot N accumulation were similar at 18/12°C and 24/16°C, and were higher than at 27/21°C. Shoot N concentration was not affected by preplant N treatments. The use of 20-40 kg ha⁻¹ preplant N may result in increased yield without decreasing PBNF when: 1) soil temperature remains below 15°C for at least two weeks after planting, and 2) soil nitrate level is less than 16 mg kg⁻¹. Proper assessment of the use of preplant N in alfalfa establishment requires a careful consideration of both soil temperature and soil N availability. / Graduation date: 1992

Designers use various representations to externalize their ideas, physical models being an important one. Physical models are widely used by designers and their use is promoted as an effective design tool by industry and government agencies. However, very little is known about the cognitive effects of physical models in the design process; the available guidelines are conflicting. Some researchers argue for the frequent implementation of physical models, while others observe that the use of physical models fixates designers. In light of these conflicts, the research discussed in this dissertation focuses on understanding the cognitive effects of physical models and developing guidelines for aiding designers in their implementation. A combination of controlled lab studies and qualitative studies is adopted to achieve said goal. The results from the controlled studies show that physical models supplement designers’ erroneous mental models and help them to come up with more ideas satisfying the problem requirements. These studies also demonstrate that design fixation is not inherent in physical modeling, but it is caused by the Sunk Cost Effect. According to Sunk Cost Effect, as designers spend more time building physical models of their initial ideas, they tend to fixate more to the variations of those ideas. A qualitative study on industry-sponsored projects and development cases of award-winning products further supports these results in more realistic situations. Further, the studies reported in this dissertation show that physical models can be effective tools for the mitigation of fixation to undesirable design features in a flawed example; however, these results can also depend upon the experience level of a designer in solving open-ended design problems. With these insights from the series of studies, a set of guidelines and a Model Error Reeducation Method (MERM) are formulated and tested with novice designers. MERM helps designers in identifying critical loads and interface designs they miss in their original designs, before prototyping. The results from the testing of this method show that this method is very useful in avoiding said errors in physical modeling.

Afin de mieux comprendre les sources et flux de nitrate dans la zone euphotique et le rôle potentiel de la fixation de l'azote atmosphérique dans la région du front des Açores (Atlantique nord-est subtropical), nous avons étudié la distribution du δ15N et δ18O du nitrate à six stations. Nous avons également mesuré le δ15N de l'azote organique dissous (AOD) de l'eau de surface, ainsi que la composition isotopique de l'azote particulaire (AP) exporté de 2003 à 2005 à la station KIEL276 (2000 m de profondeur). Nous observons une diminution du δ15N-NO3 et une augmentation du δ18O-NO3- à mesure que la concentration de nitrate diminue dans l'eau de surface pour la plupart des stations. Étant donné que l'assimilation du nitrate par le phytoplancton produit un enrichissement égal du δ15N et δ18O du nitrate, les anomalies des isotopes du nitrate dans l'eau de surface (Δ(15;18) jusqu'à ~-6%o) indiquent que l'assimilation du nitrate n'est pas le seul processus qui contrôle la composition isotopique du nitrate dans la zone photique et suggère qu'il y a reminéralisation d'azote atmosphérique nouvellement fixé dans les eaux de surface et sous surface. La concentration et le δ15N de l'AOD de l'eau de surface sont spatialement invariables avec des valeurs moyennes respectives de 4,7±0,5 f-µmol/L et 2,6±0,4%o (n=35), ce qui est en accord avec l'idée d'un réservoir océanique d'AOD majoritairement récalcitrant. La moyenne pondérée du δ15N de l'AP exporté (1,8±0,8%o, n=33) pendant les deux années d'échantillonnage est faible par rapport à la valeur du δ15N du nitrate dans la thermocline. Le faible δ15N de l'AP exporté, avec les anomalies isotopiques du N et O du nitrate et l'observation de ratios élevés des concentrations de nitrate par rapport au phosphate dans les eaux de surface et sous surface suggèrent fortement que la fixation de l'azote atmosphérique, étant un apport de matière organique ayant un faible δ15N, représente une composante majeure du cycle de l'azote dans l'Atlantique nord-est subtropical. Des bilans isotopiques simplifiés (pour le N et O du nitrate) indiquent que la fixation de l'azote, à un taux de 56-75 mmol N m-2 an-1, pourrait représenter jusqu'à ~40% de la production primaire exportée et être ainsi aussi importante que la diffusion verticale du nitrate à travers la thermocline pour soutenir la production nouvelle. ______________________________________________________________________________ MOTS-CLÉS DE L’AUTEUR : Fixation de l'azote, Front des Açores, Atlantique nord-est subtropical, δ15N et δ18O du nitrate, δ15N de l'azote organique dissous, δ15N de l'azote particulaire exporté.

While there is continuing interest in bioresorbable materials for orthopedic fixation devices, the major challenge in utilizing these materials in load-bearing applications is creating materials sufficiently stiff and strong to sustain loads throughout healing while maintaining fracture stability. The primary aim of this study is to quantify the degradation rate of a bioresorbable material system, then use this degradation rate to determine the material response of an orthopedic device made of the same material as healing progresses. The present research focuses on the development and characterization of a material system consisting of carbon foam infiltrated with hydroxyapatite (HA) reinforced poly(D,L-lactide)-co-poly(glycolide) (PDLGA). A processing technique is developed to infiltrate carbon foam with HA/PDLGA and material morphology is investigated. Additionally, short-term rat osteoblast cell studies are undertaken to establish a starting point for material biocompatibility. Degradation experiments are conducted to elicit the time-dependent properties of the material system at the material scale. These properties are then incorporated into computational models of an internal plate attached to a fractured human femur to design and predict the material response to applied physiological loads. Results from this work demonstrate the importance of material dissolution rate as well as material strength when designing internal fixation plates.

published_or_final_version / Medical Sciences / Master / Master of Medical Sciences

The availability of iron within the surface waters of the broad, oligotrophic West Florida shelf (WFS) controls periodic blooms of the pelagic marine cyanobacterium Trichodesmium. Summer delivery of iron (Fe), in the form of Saharan dust, alleviates this growth constraint, shifting limitation to the efficiency of phosphorus (P) cycles. Florida's rivers drain Miocene phosphorus deposits to supply the WFS with freshwater nutrient supplies at molar dissolved inorganic nitrogen/phosphate (DIN/PO4) ratios of less than 6. These diazotrophs draw upon ubiquitous stocks of dissolved nitrogen gas, once stimulated by Fe-deposition within P-replete waters of the West Florida shelf. An extensive in situ data set collected between 1998-2001 (NEGOM / ECOHAB / HyCODE) provided plankton taxonomy, hydrographic, nutrient, DOM, pigment, and optical properties on the shelf. A three-dimensional numerical model was constructed to analyze the impact of iron fertilization of the diazotroph Trichodesmium and the resultant effect upon the elemental cycles of N, P, and Fe. Based on the results of the coupled physical and ecological models, wet deposition of Fe-rich Saharan dust was necessary to stimulate enough nitrogen fixation to support the toxic red tide (Karenia brevis) of ~20 micrograms chl per liter found in October 1999. Ultimately, the magnitude and longevity of the Trichodesmium population, and therefore 'new' nitrogen production, was controlled by both phosphorus and iron availability.

A previously un-described filamentous non-heterocystous cyanobacterium was isolated from the South China Sea. Molecular phylogenetic analyses together with morphological observations suggested that this organism should be assigned a new specific epithet. It was designated as Leptolyngbya nodulosa Li et Brand. Filaments were enclosed in a sheath, and were unusual in their flattened appearance as seen in cross section and in the frequent occurrence of a void space (as seen by transmission electron microscopy) between the trichome and the sheath. A distinctive feature of L. nodulosa was the presence, under low light intensities, of previously un-described multicellular structures (nodules). A L. nodulosa nodule consists of a portion of a filament folded and twisted into a distinct unit surrounded by a firm continuous sheath. Nodules were highly variable in size and shape, and occurred at irregular intervals along the filament. They disappeared from filaments of cultures grown at relatively high light intensities. L. nodulosa cultures could be grown indefinitely in media devoid of any source of combined nitrogen. Acetylene reduction assays showed that L. nodulosa cultures fix dinitrogen in the dark period of a diurnal cycle under microoxygenic conditions. The addition of DCMU ([3-(3,4-dichlorophenyl)-1,1-dimethylurea], an inhibitor of Photosystem II) to a culture of L. nodulosa induced much higher rates of dinitrogenase activity and altered the cycle of activity such that most acetylene reduction occurred during the light. Measurements of dinitrogenase activity in the presence of chloramphenicol (an inhibitor of protein synthesis) indicated that dinitrogenase is synthesized in darkness and destroyed in the subsequent light period. In the presence of DCMU, a much higher dinitrogenase activity is measured, but in this case only in the light. Neither the dark-mediated dinitrogenase in the absence of DCMU nor the light-mediated activity in the presence of DCMU could be sustained for more than two days without a photoperiodic light/dark cycle. Dinitrogenase activity occurred only in non-axenic cultures of L. nodulosa. A single nifH gene, with an identical sequence in axenic and non-axenic cultures, was isolated. The requirement of heterotrophic bacteria for dinitrogenase activity in L. nodulosa is not yet understood.