Mechanistic and reactivity studies of bent metallocene complexes of niobium and tantalum

A variety of olefin hydride complexes of niobium and tantalum has been prepared in order to study their reactivity and to gain insight into organometallic reaction mechanisms. Examination of a series of ethylene and propylene complexes of niobocene (CP_2Nb; Cp = η^5-C_5H_5), permethylniobocene (Cp*_2Nb; Cp* = η^5-C_5(CH_3)_5), tantalocene, and permethyltantalocene has indicated that there are both large electronic and steric effects deriving from the metal (and its ancillary ligands) in the olefin insertion (β-migratory insertion) process. Furthermore, a thermodynamic and kinetic analysis has been completed for a series of substituted styrene complexes of niobocene in order to better understand the important electronic properties of the olefin. The results are in accord with a concerted four-center process with only moderate charge development.

The special case of β-migratory insertion of a hydride ligand into coordinated benzyne has also been studied for the permethyltantalocene system. The coordinatively unsaturated (sixteen electron) phenyl tautomer, which is made accessible by the facile benzyne hydride insertion reaction, readily reacts with a variety of ligands, L, to afford Cp*_2 Ta(C_6H_5)L complexes (L = CO, O_2, NC≡R, :CH_2, H_2, etc.). This family of compounds exhibits interesting reactivity (a-migratory insertion, O_2 activation, and reductive elimination) which is discussed in some detail.

Finally a series of paramagnetic seventeen electron Cp*_2 TaX_2 (X = halide, alkyl, hydride) complexes, and the corresponding cationic and anionic species, have been prepared and studied. The odd electron neutral complexes exhibit surprising thermal stability and undergo very little reactivity. While the chemistry of the anionic compounds is almost completely dominated by their potent reducing power, that of the cations is quite diverse and amenable for study. Therefore the syntheses and reactivity (1 ,2-eliminations, ligand insertions, and deprotonation reactions) of these coordinatively unsaturated sixteen electron species are presented.

Arctic charr (Salvelinus alpinus) in Windermere (Cumbria)

The Arctic charr of the British Isles are all non-migratory and are near their most southernmost range. Windermere is one of the few lowland lakes at southerly latitudes to contain a substantial proportion of Arctic charr. The first recorded mention of charr in Windermere was made around 1540 but it was not till the 17th century that different "sons" of charr were recognized, based on differences in their breeding behaviour. In the 1960's, the presence of two distinct populations, autumn spawners and spring spawners were discovered. In the 1980's it was shown that there were at least four races of charr in Windermere, based on genetic characteristics. Recently, the lake has changed due to inputs of phosphorus from treated sewage released into the lake resulting in eutrophication particularly in the south basin. Since the mid-1980's the numbers of charr caught in the south basin have declined.

Caracterização geológica da ocorrência de óleo na Formação Rio Bonito associada a um modelo não convencional de geração

O trabalho teve como escopo a caracterização geológica, em termos estruturais e estratigráficos, do sistema petrolífero responsável pela ocorrência de óleos encontrados na Formação Rio Bonito, na região carbonífera de Santa Catarina. Atualmente, especula-se que a assinatura geoquímica destes óleos relaciona-se à Formação Irati associado a um modelo não convencional de geração, vinculando a maturação térmica à intrusão de diabásio, devido a um soterramento insuficiente da rocha geradora. Como a Formação Irati encontra-se posicionada estratigraficamente acima da Formação Rio Bonito, o sistema está associado a um forte controle estrutural para o modelo de migração. A preparação de um mapa geológico integrado para a área de estudo envolvendo dados geológicos de campo, dados aeromagnetométricos e informações de furos de sondagem permitiu um entendimento mais aprofundado do arcabouço tectônico-estratigráfico da região. Seções geológicas mostraram a presença de falhas de grandes rejeitos que promoveram um sistema de Horsts e Grabens relacionados às NE-SW e secundariamente a falhas E-W, que permitiram a colocação da Formação Irati em contato lateral ou em um posicionamento abaixo da Formação Rio Bonito. A partir das seções cronoestratigráficas elaboradas foi possível reconhecer prováveis selos, trapas estratigráficos e estruturais, associados ao sistema petrolífero Irati-Rio Bonito. A análise geoquímica (isótopos e biomarcadores) dos óleos coletados na Formação Rio Bonito apontaram que os mesmos estão associadas aos folhelhos do Membro Assistência da Formação Irati, por possuírem uma razão pristano/fitano menor que 1, gamacerano, e a presença de isoprenóides pentametileicosano (i-25) e esqualano (i-30). A partir de análises geoquímicas realizadas em extratos orgânicos extraídos de folhelhos da Formação Irati intrudidos por diabásio, obteve-se valores da relação entre biomarcadores correspondentes e valores de Ro que indicam que foi alcançado o pico de geração de óleo. Contudo, não há registro na área de estudo de um soterramento suficiente que favorecesse essa situação, levando-nos, assim, a acreditar em um modelo de geração não convencional, por meio da intrusão de diabásio nas rochas geradoras. O arcabouço estrutural e os óleos estudados na região sugerem um processo migratório de sudoeste para o nordeste, ao longo de um sistema de falhas NE-SW, encontradas na região, que foram geradas anteriormente ou concomitantemente ao derrame basáltico associado à Formação Serra Geral.

Rotas migratórias, áreas de uso intenso e padrões de mergulho de tartarugas-de couro (Dermochelys coriacea) no Atlântico Sul Ocidental

As tartarugas marinhas são espécies ameaçadas, altamente migratórias que apresentam um ciclo de vida longo e uma ampla distribuição geográfica. Assim, melhorar a nossa compreensão sobre a ecologia espacial das tartarugas marinhas é essencial para a elucidação de aspectos da sua história de vida e para o desenvolvimento de medidas eficazes de conservação. Esta tese compreende um conjunto de artigos ou capítulos que visam contribuir ao conhecimento da ecologia espacial da tartaruga-de-couro, Dermochelys coriacea. Este estudo utilizou novas tecnologias como à telemetria por satélite (que proporciona um método útil para monitorar os movimentos de espécies migratórias) e um conjunto de ferramentas de geoprocessamento como abordagem metodológica que visou: examinar os movimentos e migrações da tartaruga-de-couro, identificar áreas de uso intenso e padrões espaço-temporais no uso do habitat, e integrar dados biológicos e oceanográficos para descrever as estratégias comportamentais desta espécie. Cinco tartarugas-de-couro (um subaduto, dois machos adultos e duas fêmeas adultas) foram equipadas com transmissores por satélite no Atlântico Sul Ocidental entre 2005 e 2008. Além de fornecer dados de localização geográfica os tansmissores permitiram registrar informações de mergulho tais como profundidade e duração máxima e media dos mergulhos, perfis completos de mergulhos individuais e dados de temperatura do mar. Movimentos e migrações de tartarugas-de-couro marcadas no Atlântico Sul foram documentados pela primeira vez. Alem disso, foi posível identificar áreas de uso intenso (ou alimentação) previamente desconhecidas para a espécie, assim como uma residência sazonal nestas áreas localizadas em águas tropicais e temperadas fora da costa sul-americana (19-45S). A sazonalidade dos movimentos esteve intimamente associada a processos físicos sazonais de pequena e mesoescala. Dependendo do ambiente marinho explorado, durante os períodos de residência, as tartarugas apresentaram diferentes estratégias alimentares identificadas através da análise dos padrões de mergulho.

Monica Alis Brick Lane: A tale of two cities or How Nazneen left her fate

O objetivo desta dissertação é analisar o romance Brick Lane (2003), da escritora Monica Ali, focalizando o processo de empoderamento da protagonista Nazneen. Usando os conceitos de lugar e não-lugar propostos por Marc Augé, pretendo examinar passagens do romance que caracterizem a sensação de não-pertencimento vivida pela personagem. Nazneen recorre às memórias de sua infância com a irmã Hasina em Bangladesh para tentar se distanciar do espaço físico de Brick Lane (a comunidade onde reside em Londres), que se constitui em um não-lugar, pois ali não é possível reconstruir sua identidade fragmentada pelo deslocamento de uma cultura para outra. Considerando aspectos históricos e culturais de Bangladesh, terra natal de Nazneen, este trabalho pretende discutir as experiências da protagonista e de outros sujeitos diaspóricos do romance, além de analisar o papel crucial que Hasina (e suas cartas) desempenham na narrativa. O atual contexto multicultural e cosmopolita da cidade de Londres também será investigado, com a discussão de situações que afetam os imigrantes e suas representações no romance. Esta dissertação também considera o caráter gendrado dos movimentos migratórios contemporâneos que possibilitam novas perspectivas acerca das consequências da diáspora. A análise de passagens selecionadas do romance ratifica o processo gradual de autonomia de Nazneen que, por fim, consegue se sentir em casa novamente

Importance de certaines caractéristiques biologiques dans la structuration génétique des espèces de poissons: le cas de Ethmalosa fimbriata et Sarotherodon melanotheron

Six populations of Ethmalosa fimbriata and six of Sarotherodon melanotheron have been analysed using enzymatic electrophoresis. The study of gene flow intensity in these two species indicate that: - In Ethmalosa fimbriata, a migratory species with high fecundity and pelagic eggs, there is a high gene flow between populations (3 Nm 83). - In Sarotherodon melanotheron, a sedentary and mouthbrooder species with low fecundity, there is a low gene flow between populations (1 Nm 4).

Estudo de ancestralidade através de marcadores genéticos uniparentais

A chegada dos primeiros habitantes há cerca de 15.000 anos e de colonos portugueses e escravos africanos, desde o século 15, em sucessivas migrações na América do Sul, levaram à formação de populações miscigenadas com raízes consideravelmente diversificadas. É notável a heterogeneidade populacional decorrente dessas migrações e do processo de amalgamento de indígenas a partir dos contatos entre os diferentes grupos étnicos, iniciados com a colonização da América pelos europeus. A despeito da elevada miscigenação, ainda se pode encontrar no Brasil populações que, majoritariamente, mantém a identidade genética dos seus ancestrais mais remotos. O objetivo desse estudo foi caracterizar a ancestralidade da população de Santa Isabel do Rio Negro, Amazonas, com fortes traços fenotípicos ameríndios, e da tribo indígena Terena de Mato Grosso do Sul. Para isto, foram estudados marcadores uniparentais paternos ligados à região não recombinante do cromossomo Y e maternos presentes na região controle do DNA mitocondrial (mtDNA). Em relação à herança paterna, foram genotipados 31 indivíduos de Santa Isabel do Rio Negro, sendo que os Terena já haviam sido estudados sob este aspecto. Quanto ao mtDNA, foram estudados 76 indivíduos de ambos os sexos e 51 Indivíduos do sexo masculino de Santa Isabel do Rio Negro e dos Terena, respectivamente. A análise de marcadores Y-SNPs possibilitou a caracterização de 55% dos cromossomos Y dos indivíduos de Santa Isabel do Rio Negro como pertencentes ao haplogrupo Q1a3a*, característico de ameríndio. Através do mtDNA, foi verificado que o haplogrupo A é o mais frequente nas duas populações, com percentuais de 34% e 42% em Santa Isabel do Rio Negro e na tribo Terena, respectivamente, observando-se no tocante à ancestralidade materna a não ocorrência de diferenciação genética significativa entre as duas populações. Por outro lado, a análise do cromossomo Y revelou a ocorrência de distância genética significativa entre elas, o que pode ser resultante da diferença entre os tamanhos das amostras populacionais ou refletir diferenças entre rotas migratórias dos ameríndios anteriormente à colonização. Os resultados mostram ainda que os genomas mitocondriais autóctones foram melhor preservados, e que novos haplogrupos do cromossomo Y foram introduzidos recentemente na população ameríndia. É, portanto, possível concluir que a população de Santa Isabel do Rio Negro e a tribo indígena Terena apresentam um significativo grau de conservação da ancestralidade ameríndia, apesar do longo histórico de contato com europeus e africanos, os outros povos formadores da população brasileira.

Evolución de las estrategias de localización residencial.Un caso de estudio Bizkaia

En las dos últimas décadas, en el territorio histórico de Bizkaia al igual que en otras muchas zonas, se observa un fenómeno de expansión de la ciudad hacia sus entornos más próximos primero, y más alejados después. En el espacio de estudio, en concreto, se trata de movimientos migratorios con origen en una zona urbana como es el Gran Bilbao y con destino las zonas rurales adyacentes a la misma. Sin embargo, no todas las zonas limítrofes muestran el mismo grado de atracción, mientras unas se han revelado como focos de atracción residencial, otras han conocido el proceso inverso. En este estudio se profundiza en el tema, a partir del análisis de las variables más relevantes que explican el fenómeno, tanto socio-demográficas, económicas, residenciales como urbanísticas.

The River Lune strategic stock assessment survey 1991 with particular reference to salmonids

In the past stock assessment surveys were generally reactive in response to a particular problem e.g. a pollution incident and as such were limited in the information they provided. A programme of strategic stock assessment would be more beneficial, providing up to date information on the status and composition of the stock. On a national level this could reveal trends in population dynamics and enable comparisons to be made between key rivers and between regions. The Stock Assessment Task Group (1991) has recommended annual strategic surveys for juvenile salmonids and triennial strategic surveys for coarse fish and non- migratory salmonids. The aim of this pilot study was to gain information on species distribution and their relative abundance within the River Lune catchment, and to compare the findings with the surveys carried out between 1981-1985. This would provide valuable information on the current status of the stock and provide an indication of the resources required to conduct such strategic surveys on other river catchments in the North West Region of the National Rivers Authority.

A report on the population structure of adult salmon and sea trout in the River Lune using scale samples - with reference to historical data.

During 1993, a comprehensive data set of scale readings, length and weight measurements was established for migratory salmonids on the River Lune. This information was collected using three methods of fish capture: 1. The Lune estuary commercial nets. 2. River Lune Forge weir fish trap. 3. River Lune rod catch scale returns. Additional information was contributed by the Kent, Leven and Duddon rod and commercial fisheries. The data shows that the salmon stock in 1993 was dominated by two year old smolts. This varies from year to year. The sea trout population displays a normal population curve in terms of numbers of fish in each age and weight class. The growth rate of salmon and sea trout is very similar even though salmon have the benefit of high sea feeding.

An investigation of the recaptures rates for tagged brown trout stocked into the River Ribble

The angling season for non-migratory brown trout, in the Environment Agency (EA) North West Region, runs from March 15th to September 30th. Each year, large numbers of farm reared brown trout are stocked into the rivers of the North West Region's Central Area. In 1994, approximately 20,000 brown trout were introduced into the River systems of the Lune, Wyre and Ribble by local angling clubs and fishery owners. Most of these fish were stocked at a length greater than that defined by local byelaws as the takeable size (200mm). Introductions are made to supplement the existing wild brown trout populations within the river and increase the probability of an angler catching a fish. Stocking with fish of a sufficient length allows the successful angler to remove the catch for their own use. In this way, stretches of the rivers are effectively managed as "put and take" fisheries for brown trout. A number of brown trout fingerlings are also introduced each year by angling clubs and fishery owners. These are stocked with the expectation that the fish will survive in the river to grow, over-winter, and eventually attain a takable size with an increased degree of "wildness". The lower cost of fingerlings, as opposed to trout of a takable length, makes their introduction more attractive to angling clubs since a greater number can be stocked for a given cost. Although the practise of stocking brown trout has occurred for many years in the Central Area, there is little information of its success in terms of increasing anglers catches, or the survival offish introduced. This study was initiated to determine the recapture rates by angling of brown trout following their introduction into a river fishery. The information gained from this study can then be used to give guidance to angling clubs and fishery owners on the optimal strategies for stocking fish.

River Wyre salmon and sea trout spawning habitat restoration / creation project. Final report April 1995

Adult salmon and sea trout rod catches in the River Wyre have been subject to considerable variability over the years. Annual rod catches ranging from 6 to 401 have been reported since records began in 1905. It has long been suspected that the physical nature of the catchment, combined with anthropogenic influences, has resulted in a deleterious effect on the Wyre fishery. Acidification problems in the head water streams (Marshaw Wyre and Tarnbrook Wyre) have been reported and are thought to threaten salmon juvenile survival. The construction of Abbeystead Reservoir and an increased tendency towards rapidly rising water levels during storms (flashiness) 1 are thought to have a significant impact on spawning gravel quality and quantity, both of which are thought to be deteriorating. As part of an overall desire to maintain and improve the migratory salmonid population in the River Wyre, this project has been commissioned to investigate remedial action which may improve and enhance spawning success, leading to an eventual improvement in the status of adult stocks. The primary objective is to establish whether the quantity and/or quality of available spawning gravels are limiting migratory salmonid productivity. The investigations undertaken confirm the general observation that useable spawning gravels appear to be in short supply in the River Wyre, and may be the limiting factor influencing returning adult stock.

Arctic charr from Ennerdale water - relicts of the ice age

The work discussed in this report deals with aspects of the ecology of Arctic charr (Salvelinus alpinus, L.). The main aims of the study were: (1) To assess the relative abundance of migrants entering the River Liza and Smithy Beck in the English Lake District). (2) To assess the degree of stream specificity. (3) To determine the period of residency in the streams. (4) To obtain a better understanding of migratory behaviour. (5) To determine the growth rate of mature fish. (6) To determine the morphometric and meristic attributes. In conjunction with this work a study was carried out to investigate the feasibility of using a video recording system to monitor the migration of charr in Smithy Beck.

Swanside Beck, fisheries survey, 22nd September 1992

Swanside Beck is formed from a number of minor tributaries which rise in the Middop area to the west of Barnoldswick. The Beck is approximately 10 km long from the source of its longest tributary (SD. 850445) to the confluence with the River Ribble (SD. 769455). Swanside Beck has one major tributary, Ings Beck, which rises from a number of sources on Twiston Moor and is approximately 6km in length from the source of its longest tributary (SD. 812418) to the confluence with Swanside Beck (SD. 785453). Both Swanside and Ings Becks are important spawning and nursery areas for salmon and sea trout from the River Ribble. In recent years a perceived decline in the migratory fish population of the becks has been reported. This decline has been reported in terms of both adult returns and juvenile production and has been particularly noted in Swanside Beck. The aim of this survey was to assess the likely benefits to Fisheries and Conservation interests of the adoption of a set aside policy for agricultural land adjacent to Swanside Beck. The survey also formed part of an on-going Fisheries study of factors limiting juvenile migratory salmonid production in Swanside Beck. This section of the report deals with the Fisheries aspects of the survey.

Electric fishing survey of the gravel addition sites on the River Wyre, Grizedale Beck and Joshua's Beck.

Although geographically the River Wyre lies between two rivers containing major migrations of adult salmon and sea trout, its rod & line fisheries have for a number of years produced exceptionally low catches. In order to determine the causes of this the Wyre Salmon and Sea trout Restoration Group (WSSRG) was conceived in 1994 as a partnership between the then National Rivers Authority (now Environment Agency), local landowners, angling clubs and interested parties. Two studies of 1994 and 1995 stated that there is a shortage of useable spawning gravels on the river. This is compounded by Abbeystead Reservoir acting as a gravel trap, the siltation of gravels on several side becks and problems with access to available gravels by returning adults. There was also perceived to be a need for accurate fishery data from the river encompassing redd counts, catch data and surveys of fry populations. The 1995 report suggested a number of management proposals which might be adopted in order to improve and create available spawning habitat for migratory salmonids. Funding was made available to create three spawning gravels on each of two side becks (Grizedale Beck and Joshua's Beck) and the addition of gravels to a site oh the main river below Abbeystead Reservoir. Modifications were also made to the fish pass at Abbeystead to allow easier passage of fish. These improvements were made in the autumn of 1995. Salmonid spawning redd counting was undertaken on the whole Wyre catchment in 1995/1996 and specific surveys by electric fishing on the gravel enhancement sites in the summer of 1996. This report details the current state of the improvement works that were undertaken and presents the results of electric fishing surveys in September 1996. A number of lessons have been learnt which will be of great benefit to the Fisheries Function in other parts of the Wyre catchment and the Central Area in general.