Manganese: Minerals, Microbes, and the Evolution of Oxygenic Photosynthesis

Oxygenic photosynthesis fundamentally transformed our planet by releasing molecular oxygen and altering major biogeochemical cycles, and this exceptional metabolism relies on a redox-active cubane cluster of four manganese atoms. Not only is manganese essential for producing oxygen, but manganese is also only oxidized by oxygen and oxygen-derived species. Thus the history of manganese oxidation provides a valuable perspective on our planet’s environmental past, the ancient availability of oxygen, and the evolution of oxygenic photosynthesis. Broadly, the general trends of the geologic record of manganese deposition is a chronicle of ancient manganese oxidation: manganese is introduced into the fluid Earth as Mn(II) and it will remain only a trace component in sedimentary rocks until it is oxidized, forming Mn(III,IV) insoluble precipitates that are concentrated in the rock record. Because these manganese oxides are highly favorable electron acceptors, they often undergo reduction in sediments through anaerobic respiration and abiotic reaction pathways.

The following dissertation presents five chapters investigating manganese cycling both by examining ancient examples of manganese enrichments in the geologic record and exploring the mineralogical products of various pathways of manganese oxide reduction that may occur in sediments. The first chapter explores the mineralogical record of manganese and reports abundant manganese reduction recorded in six representative manganese-enriched sedimentary sequences. This is followed by a second chapter that further analyzes the earliest significant manganese deposit 2.4 billon years ago, and determines that it predated the origin of oxygenic photosynthesis and thus is supporting evidence for manganese-oxidizing photosynthesis as an evolutionary precursor prior to oxygenic photosynthesis. The lack of oxygen during this early manganese deposition was partially established using oxygen-sensitive detrital grains, and so a third chapter delves into what these grains mean for oxygen constraints using a mathematical model. The fourth chapter returns to processes affecting manganese post-deposition, and explores the relationships between manganese mineral products and (bio)geochemical reduction processes to understand how various manganese minerals can reveal ancient environmental conditions and biological metabolisms. Finally, a fifth chapter considers whether manganese can be mobilized and enriched in sedimentary rocks and determines that manganese was concentrated secondarily in a 2.5 billion-year-old example from South Africa. Overall, this thesis demonstrates how microbial processes, namely photosynthesis and metal oxide-reducing metabolisms, are linked to and recorded in the rich complexity of the manganese mineralogical record.

Recolonisation of temporary streams and evolution of a degree of stability of the zoocenose [Translation from: Ecologia Mediterranea No.1 149-164, 1976]

When flow returns to a temporary stream a certain number of plant and animal species establish themselves more or less rapidly on the stream-bed constituting the initial phase of evolution of the re-population. This phase is essentially characterised by the ”awakening” of animal species that passed the dry season in a dormant state and by the development of the first unicellular algae that constitute the periphyton. Then they are succeeded by more or less stable animal groups and the structural complexity increases. The authors of the present study aim to analyse the dynamics of community succession from the return of water to the biotope until its drying up. It is attempted to determine the influence of the duration of flow on this evolution. This work is based on the analysis of population diversity with reference to its two complementary aspects, species richness and equitability. The River Destel which was studied for this project is situated in the Gorge of Ollioules near the town of Toulon.

Polaron hopping in olivine phosphates studied by nuclear resonant scattering

Valence fluctuations of Fe²⁺ and Fe³⁺ were studied in a solid solution of Li_xFePO₄ by nuclear resonant forward scattering of synchrotron x rays while the sample was heated in a diamond-anvil pressure cell. The spectra acquired at different temperatures and pressures were analyzed for the frequencies of valence changes using the Blume-Tjon model of a system with a fluctuating Hamil- tonian. These frequencies were analyzed to obtain activation energies and an activation volume for polaron hopping. There was a large suppression of hopping frequency with pressure, giving an anomalously large activation volume. This large, positive value is typical of ion diffusion, which indicates correlated motions of polarons, and Li⁺ ions that alter the dynamics of both.

In a parallel study of Na_xFePO₄, the interplay between sodium ordering and electron mobility was investigated using a combination of synchrotron x-ray diffraction and nuclear resonant scattering. Conventional Mossbauer spectra were collected while the sample was heated in a resistive furnace. An analysis of the temperature evolution of the spectral shapes was used to identify the onset of fast electron hopping and determine the polaron hopping rate. Synchrotron x-ray diffraction measurements were carried out in the same temperature range. Reitveld analysis of the diffraction patterns was used to determine the temperature of sodium redistribution on the lattice. The diffraction analysis also provides new information about the phase stability of the system. The temperature evolution of the iron site occupancies from the Mossbauer measurements, combined with the synchrotron diffraction results give strong evidence for a relationship between the onset of fast electron dynamics and the redistribution of sodium in the lattice.

Measurements of activation barriers for polaron hopping gave fundamental insights about the correlation between electronic carriers and mobile ions. This work established that polaron-ion interactions can alter the local dynamics of electron and ion transport. These types of coupled processes may be common in many materials used for battery electrodes, and new details concerning the influence of polaron-ion interactions on the charge dynamics are relevant to optimizing their electrochemical performance.

A paleoictiofauna da Formação Missão Velha, Cretáceo Inferior da Bacia do Araripe, Nordeste do Brasil

A Bacia sedimentar do Araripe é uma das mais ricas localidades fossilíferas do mundo e representa algumas das principais fases da evolução tectônica ligadas ao processo de abertura do Atlântico Sul. Essa bacia se subdivide em dois pacotes estratigráficos distintos: o Grupo Cariri (constituído pelas formações Cariri, Missão Velha e Rio Batateiras) e o Grupo Araripe (constituído pelas formações Crato, Ipubi, Santana e Exu). No caso do Grupo Cariri, apenas a Formação Missão Velha (= Brejo Santo para alguns autores) apresenta restos de peixes fósseis. Essa fauna, típica da fase rift da separação da parte oeste do Gondwana, pode ser comparada à ictiofauna já descrita no Grupo Bahia e à fauna encontrada em diversas bacias interiores do Nordeste do Brasil. O presente trabalho constou da realização de coletas na Formação Missão Velha, identificação, preparação e descrição dos espécimes coletados; comparação da paleoictiofauna dessa formação com a de outras bacias de mesma idade; análise da distribuição paleobiogeográfica dos grupos ali presentes. Apesar de desarticulados, foram identificados seis táxons de peixes, assim como fragmentos de teleósteos não identificados. Os táxons identificados a partir do material coletado são: dentes, espinhos cefálicos e espinhos de nadadeira dorsal de Hybodontiformes; escamas, dentes e ossos desarticulados de Lepidotes sp.; escamas de Pleuropholidae; diversos ossos desarticulados de Mawsonia cf. gigas; placa dentária e outros ossos isolados de Ceratodus sp. Essa fauna é muito importante, pois representa uma biota lacustrina do Neocomiano do Brasil, depositada durante os estágios pré-rift/rift da separação do oeste do Gondwana. Durante a fase pré-rift e rift pode ser observada uma correlação estratigráfica entre a Formação Missão Velha e as bacias marginais da África ocidental. Portanto, a biota presente na Formação Missão Velha auxilia a compreensão da diversidade faunística presente nos estágios pré-rift e rift do Brasil e da África.

Weighted least-squares phase unwrapping algorithm based on derivative variance correlation map

Among different phase unwrapping approaches, the weighted least-squares minimization methods are gaining attention. In these algorithms, weighting coefficient is generated from a quality map. The intrinsic drawbacks of existing quality maps constrain the application of these algorithms. They often fail to handle wrapped phase data contains error sources, such as phase discontinuities, noise and undersampling. In order to deal with those intractable wrapped phase data, a new weighted least-squares phase unwrapping algorithm based on derivative variance correlation map is proposed. In the algorithm, derivative variance correlation map, a novel quality map, can truly reflect wrapped phase quality, ensuring a more reliable unwrapped result. The definition of the derivative variance correlation map and the principle of the proposed algorithm are present in detail. The performance of the new algorithm has been tested by use of a simulated spherical surface wrapped data and an experimental interferometric synthetic aperture radar (IFSAR) wrapped data. Computer simulation and experimental results have verified that the proposed algorithm can work effectively even when a wrapped phase map contains intractable error sources. (c) 2006 Elsevier GmbH. All rights reserved.

Padrões geoacústicos de fundo e sub-fundo na Baía de Sepetiba: implicações no conhecimento da geologia do holoceno

A Baía de Sepetiba, localizada entre a Baía de Guanabara e a Baía de Ilha Grande, Estado do Rio de Janeiro, está inserida em um cenário estratégico para o desenvolvimento econômico do Estado. Isto ocorre devido ao aumento da concentração populacional, que está diretamente relacionado com o turismo, com a presença de portos e de áreas industriais. Sendo assim, se faz necessário estudar sua estrutura geológica e dinâmica sedimentar para entender sua evolução ao longo do tempo e para uma utilização mais racional desta área. Utilizando-se da sísmica rasa de alta resolução e da sonografia de varredura lateral juntamente com dados pretéritos de amostragem superficial de sedimentos, o presente trabalho tem como objetivo principal analisar sua geologia holocênica. A investigação, em subsuperfície, da geologia estrutural e sedimentar dessa baía, através da interpretação de 09 perfis sísmicos, baseada na determinação de diferentes tipos de ecotexturas, revelou a presença de diferentes pacotes sedimentares depositados ao longo do Holoceno. Ao todo, foram encontrados 15 tipos de ecotexturas perfazendo 14 camadas sedimentares, que estão relacionados em 4 Grupos de acordo com sua distribuição. Já a investigação em superfície através dos registros sonográficos, baseada nos diferentes graus de reflexão acústica (backscattering) e parametrizada pelos dados de amostragem direta pretérita, identificou 6 padrões sonográficos distintos. Com isso foi confeccionado um novo mapa de distribuição textural dos sedimentos superficiais da Baía de Sepetiba. Com a correlação dos dados de sísmica rasa com os dados sonográficos, foi possível ainda sugerir a provável existência de neotectonismo na área de estudo.