An evaluation of trace metal distribution, enrichment factors and risk in sediments of a coastal lagoon (Ria de Aveiro, Portugal)

This paper describes a sediment survey undertaken to unravel patterns of distribution and dispersion of trace metals in an Iberian Peninsula northwestern coastal lagoon (Ria de Aveiro). Cadmium, lead, chromium, copper and zinc were analyzed in bottom sediments. Geochemical normalization is performed and two different regression models for each metal versus aluminum are tested and compared using the respective enrichment factors (EF), an estimation of the relative importance of anthropogenic contributions to the studied sediments. Mean sediment quality guideline quotients (mSQGQ) are used to evaluate sediment quality and associated potential risk to biota with effects range low as empirical sediment quality guideline (SQG) in the basis for mSQGQ calculation. Additionally, the geoaccumulation index is calculated to compare studied sediment levels to global baseline levels. The application of SQGs revealed insufficient characterization capability, especially when contrasted to EF calculated from the regression methods. These pointed a mildly enriched system with localized “hot spot” areas. Therefore, it can be considered that bottom sediments in the Ria de Aveiro system are in their majority unpolluted, zinc being the only metal of concern, presenting enrichment in all four main channels. The major rivers outlets (Caster, Antuã, and Vouga) constitute point sources, thus presenting potential risk for biota. Yet, the strong tidal influence creates a damping effect by efficiently redistributing sediment bound metals.

Insight into Biological Small-Molecule Activation from Enzymes, Model Complexes, and X-ray Spectroscopy

Thesis (Ph.D.)--University of Washington, 2016-08

Ecophysiologie de la maturation sexuelle et de la ponte de l'huître creuse Crassostrea gigas : réponses métaboliques (respiration) et alimentaires (filtration, absorption) en fonction des différents stades de maturation

The study of maturation and spawning of the oyster is part of a research program to investigate the summer mortalities of the oysters, Crassostrea gigas in Marennes-Oléron Bay. Four maturity stages were simultaneously obtained by diet and thermal conditioning (immature, low maturation, mature and post-spawning stages). Measurements of clearance, filtration, absorption and respiration rates allowed a calculation of the scope for growth and hence an estimation of the oyster's energetic budget at various maturity stages. Male and female oysters had similar physiological responses. The filtration rate ranged from 2.4 to 2.6 1.h(-1) at the early stages of maturation and decreased to 1.8 1.h.' during the maturity stage. Growth rate resulting from gonad development did not induce filtration rate changes. Mature 2.5 and 1.5-year-old oysters showed a negative energy budget reaching -15 and -90 J.h(-1) respectively. By contrast, non-ripe oysters had scope for growth in the range 110 to 170 J.h(-1). A negative energy budget during the high maturation stage resulted from a reduced absorption efficiency. A new allometric relationship for the respiration model of C. gigas was defined during vitellogenesis with a 0.574 coefficient value. Based on Our results, the oyster's physiological weakness during vitellogenesis should be considered as a part of explanation for spring and summer mortalities of cultured oysters in Marennes-Oléron Bay.

Ecophysiologie de la maturation sexuelle et de la ponte de l'huître creuse Crassostrea gigas : réponses métaboliques (respiration) et alimentaires (filtration, absorption) en fonction des différents stades de maturation

The study of sexual maturation and spawning in the Pacific oyster (Crassostrea gigas) is part of a vast research programme that endeavours to understand the causes of mortality that occur sporadically during the spring and summer seasons in the Marennes-Oléron Bay. Thermal and diet conditioning were used to obtain oysters at each stage of maturity simultaneously. Using the measured rates of clearance, consumption, absorption and respiration provided estimates of growth potential and gave the energetic budget of oysters at different stages of sexual maturity. Physiological responses were similar for males and females. Filtration decreased from 2.4 to 2.6 l.h (-1) to 1.8 l.h (-1) with increasing maturity. Weight gain was associated with gonad development and did not appear to have an effect on the clearance rate. Oysters 2.5 years old showed a negative energy budget (-15 J h (-1)) at later maturity stages. This deficit was confirmed (90 J.h (-1)) in oysters 1.5 years old at the same stage of maturity. On the contrary, immature oysters, in the early stages of maturity or post-spawning, had a growth potential of 110 to 170 J.h (-1). The energy deficit observed at later stages of maturity was primarily due to absorption, which decreased sharply during peak gametogenesis. Using measured respiration rates, an allometric relationship specific to gonad growth was determined with a coefficient of 0.574. Low physiological performance of oysters, observed at later stages of sexual maturity, must be taken into account in research on the factors responsible for spring and summer mortalities affecting oyster farms in Marennes-Oléron.

Corrosion protection of PVD and paint coatings for selective solar absorber surfaces

The selective solar absorber surface is a fundamental part of a solar thermal collector, as it is responsible for the solar radiation absorption and for reduction of radiation heat losses. The surface’s optical properties, the solar absorption (á) and the emittance (å), have great impact on the solar thermal collector efficiency. In this work, two coatings types were studied: coatings obtained by physical vapor deposition (PVDs) and coatings obtained by projection with different paints (PCs) on aluminum substrates. The most common industrial high performing solar selective absorbers are nowadays produced by vacuum deposition methods, showing some disadvantages, such as lower durability, lower resistance to corrosion, adhesion and scratch, higher cost and complex production techniques. Currently, spectrally selective paints are a potential alternative for absorbing surfaces in low temperature applications, with attractive features such as ease of processing, durability and commercial availability with low cost. Solar absorber surfaces were submitted to accelerated ageing tests, specified in ISO 22975-3. This standard is applicable to the evaluation of the long term behavior and service life of selective solar absorbers for solar collectors working under typical domestic hot water system conditions. The studied coatings have, in the case of PVDs solar absorptions between 0.93 and 0.96 and emittance between 0.07 and 0.10, and in the case of PCs, solar absorptions between 0.91 and 0.93 and emittance between 0.40 and 0.60. In addition to evaluating long term behavior based on artificial ageing tests, it is also important to know the degradation mechanism of different coatings that are currently in the market. Electrochemical impedance spectroscopy (EIS) allows for the assessment of mechanistic information concerning the degradation processes, providing quantitative data as output, which can easily relate to the kinetic parameters of the system. EIS measures were carried out on Gamry FAS2 Femostat coupled with a PCL4 Controller. Two electrolytes were used, 0.5 M NaCl and 0.5 M Na2SO4, and the surfaces were tested at different immersion times up to 4 weeks. The following types of specimens have been tested: Aluminium with/without surface treatment, 3 selective paint coatings (one with a poly(urethane) binder and two with silicone binders) and 2 PVD coatings. Based on the behaviour of the specimens throughout the 4 weeks of immersion, it is possible to conclude that the coating showing the best protective properties corresponds to the selective paint coating with a polyurethane resin followed by the other paint coatings, whereas both the PVD coatings do not confer any protection to the substrate, having a deleterious effect as compared to the untreated aluminium reference.

Organic acids in Kakadu plum (Terminalia ferdinandiana): The good (ellagic), the bad (oxalic) and the uncertain (ascorbic)

The phenolic ellagic acid (EA) is receiving increasing attention for its nutritional and pharmacological potential as an antioxidant and antimicrobial agent. The Australian native Kakadu plum (Terminalia ferdinandiana) fruit is an abundant source of this phytochemical. The fruit also contains large amounts of vitamin C (mainly as ascorbic acid, AA) and possibly the undesirable oxalic acid (OA). Regular consumption of high oxalate foods poses a variety of health risks in humans including interference with calcium absorption and kidney stone formation. Oxalate is also the end-product of AA metabolism so that consumption of fruit with heightened AA content has the potential to elevate urinary oxalate levels. The aims of this study were to investigate the distribution of EA and the presence of other bioactives in other Kakadu plum tissues. Chemical analysis of Kakadu plum fruit and leaves for EA (free and total), OA (water-soluble and total), calcium (Ca) and AA indicated that EA and AA concentrations were high in the fruit while the leaves had significantly higher EA levels but little or no detectable AA. OA content in fruit and leaves was substantial with the fruit being placed in the high-Oxalate category. These findings suggest that there is potential to elevate oxalate levels in the urine of susceptible people and intake of fruit-derived products should be closely monitored. By measuring tissues collected from specific trees, high EA-producing or low OA-containing individuals were identified.

Effect of temperature on genomic and some biological indices during embryonic and larval development of Caspian trout Salmo trutta caspius Kessler, 1877

Since 1966 especially recent decade, Caspian trout (Salmo trutta caspius Kessler, 1877) considered as a strategic endemic species for Caspian Sea fisheries resources also coldwater aquaculture in Iran. Nowadays habitat condition effects on this subspecies during life stages, artificial breeding and incubation period noticed by research and execution sessions of fisheries in Iran. Incubation duration of Caspian trout from artificial fertilization followed by green egg and eyed egg, hatching and yolk sac absorption identified as most sensitive stages for fish and any pollution, stress and deviation by natural life conditions of embryo up to larvae could provide possible mortalities and observable or hidden alterations. Among all vital factors for Caspian trout welfare even in conservation plans and stocks rehabilitation programs or recent attempts for domestication of this fish for introduction to cold water aquaculture industry, water temperature as the most important physical factor which might conserve or induce stress to rearing environment condition is not considered yet. In hatcheries activities, the temperature for incubation and rearing Caspian trout eggs is determining by available water temperature and wide range of temperatures in governmental or private farms is using depend on the water resources availability. Also global climate change consideration and increase temperature trend accompany with group of physical and chemical factors provided by fish farm discharges and other source points entered to the migration pathway of Caspian trout in spawning season were not investigated before. Natural spawning migration pathway is upstream of Caspian tout south and south west rivers especially in Cheshmehkileh upstream in Tonekabon, Iran directed this research focus on the mentioned location. For simulation of natural spawning bed for Caspian trout, water supplied from the upstream of Daryasar branch as headwater of Cheshmehkileh River which provided REDD water condition for in vitro incubation. Green eggs treatments of wild and F1 cultured brooders both 3+ were incubated. Incubation implemented in dark, constant temperature (4, 8, 12 degree centigrade) and DO–pH–temperature digital monitoring in 3 recycling incubators ended to yolk sac absorption and entering larval stage. Hatching success, possible genome alterations by HSP70 gene expression and comet assay implemented as diagnostic tools in 3 life stages of eyed egg– Alevin and Larvae. Numbers and diameters of larvae white fiber muscles measured by histology experiment and Hematoxylin–eosine staining. Results stated significant effect of incubation temperature on hatching success, genome and white fiber muscles of wild and F1 samples. Hatching success measured as 31% and 38% for cultured and wild cold treatments, 79% and 91% for normal and 64% and 73% for warm cultured and wild treatments respectively. Considerable mortality occurred for cold treatment and 8 degree centigrade stated the best thermal condition in normal incubator according to hatching success in wild Caspian trout samples.

Reduced graphene oxide and Ag wrapped TiO2 photocatalyst for enhanced visible light photocatalysis

A well-organised reduced graphene oxide (RGO) and silver (Ag) wrapped TiO2 nano-hybrid was successfully achieved through a facile and easy route. The inherent characteristics of the synthesized RGO-Ag/TiO2 were revealed through crystalline phase, morphology, chemical composition, Raman scattering, UV-visible absorption, and photoluminescence analyses. The adopted synthesis route significantly controlled the uniform formation of silver nanoparticles and contributed for the absorption of light in the visible spectrum through localized surface plasmon resonance effects. The wrapped RGO nanosheets triggered the electron mobility and promoted visible light shift towards red spectrum. The accomplishment of synergised effect of RGO and Ag well degraded Bisphenol A under visible light irradiation with a removal efficiency of 61.9%.

Imperfect indifference : the rhythm, structure and politics of neutrality

Cette thèse propose l’émergence d’une poésie de l’entre deux dans la littérature expérimentale, en suivant ses développements du milieu du vingtième siècle jusqu'au début du vingt-et-unième. Cette notion d’entre-deux poétique se fonde sur une théorie du neutre (Barthes, Blanchot) comme ce qui se situe au delà ou entre l'opposition et la médiation. Le premier chapitre retrace le concept de monotonie dans la théorie esthétique depuis la période romantique où il est vu comme l'antithèse de la variabilité ou tension poétique, jusqu’à l’émergence de l’art conceptuel au vingtième siècle où il se déploie sans interruption. Ce chapitre examine alors la relation de la monotonie à la mélancolie à travers l’analyse de « The Anatomy of Monotony », poème de Wallace Stevens tiré du recueil Harmonium et l’œuvre poétique alphabet de Inger Christensen. Le deuxième chapitre aborde la réalisation d’une poésie de l’entre-deux à travers une analyse de quatre œuvres poétiques qui revisitent l’usage de l’index du livre paratextuel: l’index au long poème “A” de Louis Zukofsky, « Index to Shelley's Death » d’Alan Halsey qui apparait à la fin de l’oeuvre The Text of Shelley's Death, Cinema of the Present de Lisa Robertson, et l’oeuvre multimédia Via de Carolyn Bergvall. Le troisième chapitre retrace la politique de neutralité dans la théorie de la traduction. Face à la logique oppositionnelle de l’original contre la traduction, il propose hypothétiquement la réalisation d’une troisième texte ou « l’entre-deux », qui sert aussi à perturber les récits familiers de l’appropriation, l’absorption et l’assimilation qui effacent la différence du sujet de l’écrit. Il examine l’oeuvre hybride Secession with Insecession de Chus Pato et Erin Moure comme un exemple de poésie de l’entre-deux. A la fois pour Maurice Blanchot et Roland Barthes, le neutre représente un troisième terme potentiel qui défie le paradigme de la pensée oppositionnelle. Pour Blanchot, le neutre est la différence amenée au point de l’indifférence et de l’opacité de la transparence tandis que le désire de Barthes pour le neutre est une utopie lyrique qui se situe au-delà des contraintes de but et de marquage. La conclusion examine comment le neutre correspond au conditions de liberté gouvernant le principe de créativité de la poésie comme l’acte de faire sans intention ni raison.

Analysis and control of transient spectra using time-dependent density functional theory.

215 p.

“In The Good Old Days of Long Ago": Echoes of Vaudeville and Minstrelsy in the Music of Uncle Dave Macon

Uncle Dave Macon provided an essential link between nineteenth-century, urban popular stage music (especially the minstrel show and vaudeville) and commercialized country music of the 1920s. He preserved through his recordings a large body of songs and banjo techniques that had their origins in urban-based, nineteenth-century vaudeville and minstrelsy. Like the minstrel and vaudeville performers of the nineteenth century, Macon told jokes and stories, employed attention-grabbing stage gimmicks, marketed himself with boastful or outrageous slogans, and dressed with individual flair. At the same time, Macon incorporated many features from the rural-based folk music of Middle Tennessee. Overall, Macon’s repertoire, musical style, and stage persona (which included elements of the rube, country gentleman, and old man) demonstrated his deep absorption, and subsequent reinterpretation, of nineteenth-century musical traditions. Macon’s career offers a case study in how nineteenth-century performance styles, repertoire, and stage practices became a part of country music in the 1920s. As an artist steeped in two separate, but overlapping, types of nineteenth-century music—stage and folk—Macon was well-positioned to influence the development of the new commercial genre. He brought together several strains of nineteenth-century music to form a modern, twentieth-century musical product ideally suited to the new mass media of records, radio, and film. By tracing Macon’s career and studying his music, we can observe how the cross-currents of rural and popular entertainment during the nineteenth and early twentieth centuries interacted to form the commercial genre we now know as country music.

Mesoscale Optoelectronic Design of Wire-Based Photovoltaic and Photoelectrochemical Devices

The overarching theme of this thesis is mesoscale optical and optoelectronic design of photovoltaic and photoelectrochemical devices. In a photovoltaic device, light absorption and charge carrier transport are coupled together on the mesoscale, and in a photoelectrochemical device, light absorption, charge carrier transport, catalysis, and solution species transport are all coupled together on the mesoscale. The work discussed herein demonstrates that simulation-based mesoscale optical and optoelectronic modeling can lead to detailed understanding of the operation and performance of these complex mesostructured devices, serve as a powerful tool for device optimization, and efficiently guide device design and experimental fabrication efforts. In-depth studies of two mesoscale wire-based device designs illustrate these principles—(i) an optoelectronic study of a tandem Si|WO3 microwire photoelectrochemical device, and (ii) an optical study of III-V nanowire arrays.

The study of the monolithic, tandem, Si|WO3 microwire photoelectrochemical device begins with development and validation of an optoelectronic model with experiment. This study capitalizes on synergy between experiment and simulation to demonstrate the model’s predictive power for extractable device voltage and light-limited current density. The developed model is then used to understand the limiting factors of the device and optimize its optoelectronic performance. The results of this work reveal that high fidelity modeling can facilitate unequivocal identification of limiting phenomena, such as parasitic absorption via excitation of a surface plasmon-polariton mode, and quick design optimization, achieving over a 300% enhancement in optoelectronic performance over a nominal design for this device architecture, which would be time-consuming and challenging to do via experiment.

The work on III-V nanowire arrays also starts as a collaboration of experiment and simulation aimed at gaining understanding of unprecedented, experimentally observed absorption enhancements in sparse arrays of vertically-oriented GaAs nanowires. To explain this resonant absorption in periodic arrays of high index semiconductor nanowires, a unified framework that combines a leaky waveguide theory perspective and that of photonic crystals supporting Bloch modes is developed in the context of silicon, using both analytic theory and electromagnetic simulations. This detailed theoretical understanding is then applied to a simulation-based optimization of light absorption in sparse arrays of GaAs nanowires. Near-unity absorption in sparse, 5% fill fraction arrays is demonstrated via tapering of nanowires and multiple wire radii in a single array. Finally, experimental efforts are presented towards fabrication of the optimized array geometries. A hybrid self-catalyzed and selective area MOCVD growth method is used to establish morphology control of GaP nanowire arrays. Similarly, morphology and pattern control of nanowires is demonstrated with ICP-RIE of InP. Optical characterization of the InP nanowire arrays gives proof of principle that tapering and multiple wire radii can lead to near-unity absorption in sparse arrays of InP nanowires.

Surface photochemistry: photodegradation study of pyrene adsorbed onto microcrystalline cellulose and silica

Ground-state diffuse reflectance, time resolved laser-induced luminescence, diffuse reflectance laser flash-photolysis transient absorption and chromatographic techniques were used to elucidate the photodegradation processes of pyrene adsorbed onto microcrystalline cellulose and silica. Ground-state diffuse reflectance showed that on both substrates low concentrations display absorption of pyrene monomers. At high concentrations spectral changes attributed to aggregate formation were observed. Laser induced fluorescence showed that pyrene onto microcrystalline cellulose mainly presents fluorescence from monomers, while for silica, excimer-like emission was observed from low surface loadings (greater than or equal to 0.5 mumol g(-1)). Transient absorption and photodegradation studies were performed at concentrations where mainly monomers exist. On silica, pyrene presents transient absorption from its radical cation. On microcrystalline cellulose both radical cation, radical anion and pyrene triplet-triplet absorption were detected. Irradiation followed by chromatographic analysis showed that pyrene decomposes on both substrates. For pyrene on microcrystalline cellulose 1-hydroxypyrene was the main identified photoproduct since in the absence of oxygen further oxidation of 1-hydroxypyrene was very slow. For pyrene on silica photodegradation was very efficient. Almost no 1-hydroxypyrene was detected since in the presence of oxygen it is quickly oxidized to other photooxidation products. On both substrates, pyrene radical cation is the intermediate leading to photoproducts and oxygen it is not involved in its formation.

Photochemistry of 4-chlorophenol on cellulose and silica

The photochemistry of 4-chlorophenol (4-CP) was studied on silica and cellulose, using time-resolved diffuse reflectance techniques and product degradation analysis. The results have shown that the photochemistry of 4-CP depends on the support, on the concentration, and also on the sample preparation method. Transient absorption and photoproduct results can be understood by assuming the formation of the carbene 4-oxocyclohexa-2,5-dienylidene in both supports. On cellulose, at concentrations lower than 10 mumol g(-1), the carbene leads to the unsubstituted phenoxyl radical, and phenol is the main degradation product. At higher concentrations a new transient resulting from phenoxyl radicals coupling was also observed, and dihydroxybiphenyls are also formed. The reaction of the carbene with ground-state 4-CP was also detected through the formation of 5-chloro-2,4'-dihydroxybiphenyl. 4-Chlorophenoxyl radical and degradations products resulting from its coupling were also detected. Oxygen has little effect on the photochemistry of 4-CP on cellulose. On silica the transient benzoquinone O-oxide was formed in the presence of oxygen. Benzoquinone and hydroquinone are the main degradation products. In well-dried samples the formation of hydroquinone is reduced. At higher concentrations the same products as detected on cellulose were observed. 4-CP undergoes slow photochemical decomposition under solar radiation in both supports. The same main degradation products were observed in these conditions.

Degradacao termica e catalitica da borra oleosa de Petroleo com materiais nanoestruturados al-mcm-41 e AL-SBA-15

Aiming to reduce and reuse waste oil from oily sludge generated in large volumes by the oil industry, types of nanostructured materials Al-MCM-41 and Al-SBA-15, with ratios of Si / Al = 50, were synthesized , and calcined solids used as catalysts in the degradation of oily sludge thermocatalytic oil from oilfield Canto do Amaro, in the state of Rio Grande do Norte. Samples of nanostructured materials were characterized by thermogravimetric analysis (TG / DTG), X-ray diffraction (XRD), scanning electron microscopy (SEM), absorption spectroscopy in the infrared Fourier transform (FT-IR) and adsorption nitrogen (BET). The characterization showed that the synthesized materials resulted in a catalyst nanostructure, and ordered pore diameter and surface area according to existing literature. The oily sludge sample was characterized by determining the API gravity and sulfur content and SARA analysis (saturates, aromatics, resins and asphaltenes). The results showed a material equivalent to the average oil with API gravity of 26.1, a low sulfur content and considerable amount of resins and asphaltenes, presented above in the literature. The thermal and catalytic degradation of the oily sludge oil was performed from room temperature to 870 ° C in the ratios of heating of 5, 10 and 20 ° C min-1. The curves generated by TG / DTG showed a more accelerated degradation of oily sludge when it introduced the nanostructured materials. These results were confirmed by activation energy calculated by the method of Flynn-Wall, in the presence of catalysts reduced energy, in particular in the range of cracking, showing the process efficiency, mainly for extraction of lightweight materials of composition of oily sludge, such as diesel and gasoline