The climatic history of the planet Earth is characterized by long- and short-term climatic variations. Oxygen isotopic data clearly shows how during the Cenozoic (from 65 Ma to the present) our planet shifted over time, from greenhouse to icehouse climate states up to the present. Along this progressive cooling, the record is dotted by rapid warming and cooling transient events, from which the causes are not yet fully understood. One problem with paleoceanographic reconstructions is that the older the event, the harder it is to find a sedimentary record in which the paleoclimatic proxies are preserved enough to be used with confidence. This work has the goal of illustrating the possibility to develop a new paleoenvironmental indicator based on the magnetic properties of magnetite crystals synthetized by magnetotactic bacteria. The sensibility of such crystals to small changes in dissolved oxygen content in the pore water and water column is well known, and can be exploited to reconstruct such changes from the sedimentary record. Qualitative information regarding this topic are defined in scientific literature, but, so far, no quantitative study has been performed. This is the first attempt to quantify the preservation of biogenic magnetite as a function of oxygenation state of waters, and is based on recent sediment extracted from cores collected in the coastal region of Rio de Janeiro (Saco do Mamanguá, Paraty). From these, where it was possible to obtain magnetic data relative to magnetite crystals together as well with as direct measurements of pore water chemistry. The results of this first attempt were used to analyze climatic and oceanographic conditions in two other sites, representative of key past environmental events during the Paleocene. The first case study was performed in a newly descripted sedimentary outcrop in central Turkey, of middle Eocene age, representative of a period of rapid warming (Middle Eocene Climatic Optimum, MECO). The second case study was done using material from a marine sediment core collected in the Ross Sea (Antarctica) that covers from the late Eocene to the Middle Miocene, a period that saw the onset of the modern, permanent ice sheet cover in the Antarctic continent. / A historia climática da Terra é caracterizada por variações climáticas de curto e longo prazo, com variações de condições, as vezes extremas. Dados de isótopos de oxigênio mostram claramente que durante o Cenozoico (desde 65 Ma até o presente) o nosso planeta passou de uma fase quente caracterizada por marcado efeito estufa (durante o Paleoceno) para um período progressivamente mais frio em direção ao presente. Ambos esses estados são caracterizados pela alternância de eventos transientes quentes e frios de relativa curta duração, sendo que destes a maioria ainda não é plenamente compreendida. Um dos principais problemas das reconstruções paleoceangráficas é que quanto mais antigo o evento mais difícil encontrar sequências sedimentares cujo registro de proxies paleoambientais seja preservado e confiável. Este trabalho visa explicitar a possibilidade de desenvolver um novo indicador paleoambiental, baseado em propriedades magnéticas de cristais de magnetita biosintetizados por bactérias magnetotáticas. Tais cristais biogênicos são notavelmente sensíveis a pequenas variações de oxigênio dissolvido na coluna de água e na agua intersticial entre os poros dos sedimentos marinhos, e essa sensibilidade pode ser explorada para reconstruir variações climáticas no registro sedimentar do passado. Informações qualitativas estão disponíveis na literatura cientifica mas, até agora, não existem estudos que quantifiquem essa relação. Esta primeira tentativa de quantificar a preservação de magnetita biogênica em função do estado de oxigenação de águas se baseia em testemunhos coletados na costa do estado do Rio de Janeiro (Saco do Mamanguá, Paraty), onde foi possível coletar dados magnéticos relativos aos cristais de magnetita biogênica concomitantemente a medidas diretas de química da água intersticial. Os resultados desse primeiro estudo foram aplicados para reconstruções de variações climáticas e oceanográficas em duas seções que registram importantes mudanças climáticas durante o Paleogeno. No primeiro caso, um afloramento localizado na Turquia central de idade Eocenica e representativo de um período de rápido aquecimento (Ótimo Climático do Eoceno Médio, Middle Eocene climatic Optimum, MECO). No segundo caso, um testemunho coletado no Mar de Ross (Antártica) que abrange o período entre o Eoceno superior e o Mioceno médio, durante o qual houve a formação da primeira cobertura de gelo permanente no continente antártico.

[Truncated abstract] Clinical magnetic resonance imaging (MRI) scanners were used to investigate the measurement and imaging of ferrimagnetic particle concentrations in biological tissues in vivo. The presence of ferrimagnetic particles tends to increase the proton transverse relaxation rate (R2) of water protons in tissue. A quantitative image of R2 can be generated using a series of single spin echo magnetic resonance images acquired using clinical MRI scanners and analysing the images using techniques based on that reported by Clark and St. Pierre (2000). If ferrimagnetic particles have a high enough concentration, there is a monotonic relationship between particle concentration and R2; therefore an image of R2 gives a map of the ferrimagnetic particle concentration in the tissue. These techniques were used to investigate the feasibility of in vivo measurement of the concentration and distribution of both synthetic and biogenic ferrimagnetic particles in tissue. Rabbit liver was loaded with ferrimagnetic particles of ?-Fe2O3 (designed for magnetic hyperthermia treatment of liver tumours) by injecting various doses of a suspension of the particles into the hepatic artery in vivo. R2 images of the livers in vivo, excised, and dissected were generated from a series of single spin-echo images. Mean R2 values for samples of ferrimagnetic-particle-loaded liver dissected into approximate 1 cm cubes were found to linearly correlate with tissue iron concentration over the range from approximately 0.1 to at least 2.7 mg Fe/g dry tissue when measured at room temperature. Changing the temperature of ferrimagnetic-particle-loaded samples of liver from 1?C to 37?C had no observable effect on tissue R2 values. However, a small but significant decrease in R2 was found for control samples containing no ferrimagnetic material on raising the temperature from 1?C to 37?C. Both chemically measured iron ii concentrations and mean R2 values for rabbit livers with implanted tumours tended to be higher than those measured for tumour-free liver. This study indicates that tissue R2 measurement and imaging by nuclear magnetic resonance may have a useful role in magnetic hyperthermia therapy protocols for the treatment of liver cancer. In order to investigate the use of clinical MRI scanners to measure biogenic ferrimagnetic particle concentrations in human brain tissue, agar gel based phantoms containing ferrimagnetic particles were made in order to determine the lower concentration detection limit for such particles in a homogenous medium. Magnetite/maghemite nanoparticles were synthesized in the presence of either dextran or polyvinyl alcohol, yielding cluster- and necklace-like aggregates, respectively. Magnetization, Mossbauer spectroscopy, and microscopy measurements indicated that the arrangement of the particles within the aggregates affects the magnetic properties of the particles resulting in smaller particles in the clusters having higher superparamagnetic blocking temperatures than larger particles in the necklaces.

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