The aim of this thesis is to develop and apply novel climate proxies to understand the palaeoceanographic evolution of the N.E. Atlantic during the late-Glacial and Holocene. The proxies investigated are based on organic molecular compounds called lipid biomarkers and bulk organic matter properties. The primary focus is on long-chain alkenones, molecules which have been extensively used in mid and low latitude open oceans to reconstruct sea surface temperatures (SSTs) during the Quaternary. Thus, the relative abundance of some alkenones is related to the growth temperature of the algae at the time of the biosynthesis of these molecules (expressed in the U(^K)(_37) and U(^K)(_37)’ indices). In high latitudes and coastal environments, the temperature dependence of alkenones is controversial, and the potential environmental information from alkenones is not yet well understood. In such locations there is increasing abundance of the C(_37:4) alkenone (quantified as %C(_37:4)). The presence of this component has been related to changes in the relative budget of freshwater in the surface ocean. A central aim of this thesis is to carry out an empirical investigation to find out the key environmental factors that control %C(_37:4) to assess its potential as a palaeoceanographic proxy. Research was conducted in the Nordic Seas and N.W. Scotland using samples from the water column, surficial sediment and sediment cores. The research undertaken can be broken down in three main sections: Alkenone distributions in the Nordic Seas. The aim was to clarify and extend the application of alkenones as palaeoceanographic proxies in subpolar to polar environments. Samples of filtered sea surface POM were analysed and extremely high %C(_37:4) values (up to 77%) were measured in polar waters (up to 80% sea-ice cover). Values of %C(_37:4) across the Nordic Seas showed a strong association with water mass type. A combined data-set revealed a stronger correlation of %C(_37:4) to sea surface salinity' (SSS, R(^2) = 0.72) than to SST (R(^2) = 0.5). However, scatter was observed in the relationship of %C(_37:4) to SSS, preventing confirmation of %C(_37:4) as a palaeo-SSS proxy. Values of %C(_37:4) in sea surface POM were high compared to surficial sediments. We discount preferential degradation of the %C(_37:4) alkenone and invoke dilution of the %C(_37:4) signal in sea surface sediments by advected allochthonous matter to explain this. The POM filter data suggest that, overall, U(^K)(_37) is a more appropriate SST index for the Nordic Seas than U(^K)(_37) '. Examination of the scatter in the U(^K)(_37) ' versus SST relationship, shows that regions in the south of the Nordic Seas (including the Icelandic shelf) may yield reliable, alkenone based, palaeoceanographic reconstructions. Comparison of %C(_37:4) distributions with dinocyst proxies in a late Holocene core from the Barents Sea suggests %C(_37:4) may be a general marker for the influence of arctic/polar water in palaeoceanographic reconstructions. The palaeoceanography of the Icelandic shelf iox. the post-Glacial period (0-15 kyr BP) was reconstructed from alkenone indices measured in three cores collected N and W of Iceland. One of the cores, JR51-GC35, contained a continuous record of Holocene sedimentation spanning 0 - 10.1 kyr BP. Superimposed on a general Holocene cooling trend in core JR5I-GC35 were millennial scale oscillations of ~2 C. The timing of the oscillations was in close agreement with the variability in IRD records from the East Greenland shelf and the timing of glacier advances in northern Iceland. A comparison of the U(^K)(_37) -SST records from JR51-GC35 and a published core from the eastern Nordic Seas (MD952011) showed significant differences (superimposed on the general trend) in the timing of millennial scale climate events. This illustrates that Holocene climate evolution in the Nordic Seas was more complex than previously suggested, with significant climatic differences between the eastern and western Nordic Seas caused by the differential variability of the Irminger and Norwegian Currents with time. The potential application for reconstructing past sea-level changes in NW. Scotland of lipid biomarkers (alkenones, n-alkanes and chlorophyll derivatives), and bulk organic parameters (%TOC, C(_nrg)/N) was assessed by a survey of modern basins (at different stages of isolation from the sea) and fossil basins (with known sea-level histories). A logit regression analysis of all the sediment samples was employed to find which of the biomarkers or bulk organic measurements could reliably characterize the sediment samples in terms of a marine/brackish or isolated/lacustrine origin. The results suggested an excellent efficiency for the alkenone index %C(_37:4) at predicting the depositional origin of the sediments. This study suggests alkenones could be used as an indicator of sea-level change in fossil isolation basins.

No description available.

O destino de grande parte da matéria orgânica presente nos oceanos é o sedimento marinho. Essa matéria orgânica, que vai sendo armazenada ao longo dos anos, produz uma reserva única de informações sobre os processos biogeoquímicos ocorridos no passado e como esses processos responderam às mudanças ambientais. Certas moléculas orgânicas são sintetizadas apenas por organismos marinhos ou somente por plantas superiores terrestres. A abundância relativa desses compostos em sedimentos marinhos pode ser usada para determinar a contribuição de matéria orgânica terrestre ou marinha que foi depositada. Outros compostos, cujas fontes naturais são raras ou inexistem, encontrados em sedimentos, refletem a influência antrópica no meio. Há ainda compostos, com origem biológica especifica, cujas estruturas são influenciadas pelo controle enzimático dos organismos que os produzem, que são influenciados pelo meio. Esses compostos, cuja presença pode fornecer evidências inequívocas da sua fonte ou informações sobre condições oceanográficas recebem o nome de marcadores biológicos e são comumentemente abreviados como biomarcadores. Esse trabalho produziu uma metodologia analítica para identificação e quantificação de biomarcadores como os hidrocarbonetos alifáticos, hidrocarbonetos policíclicos aromáticos, esteróis e alquenonas através de uma única extração lipídica. Essa metodologia foi avaliada por diversos critérios analíticos e validada através de materiais de referência e de exercícios de comparação entre laboratórios. A metodologia foi aplicada em um testemunho de sedimento marinho obtido em Cabo Frio. A quantificação das alquenonas nas amostras do testemunho permitiu estimar a variação da temperatura da superfície oceânica ao longo dos anos e correlacioná-la com variações na intensidade da ressurgência, além de permitir verificar como os demais biomarcadores variaram em função da variação da temperatura do meio onde foram sintetizados. / The fate of most organic matter in the oceans is the marine sediment. This preserved organic matter became an unique reservoir of information about the operation of biogeochemical processes in the geological past, and how these processes responded to environmental changes. Some molecules are only synthesized by sea organisms, others only by higher plants. The relative abundance among these compounds in sea sediments can be used to determine the source of the organic matter. Other organic compounds, without natural sources, are an indicative of anthropogenic influence. The marine sediment also can accumulate compounds with the specific biological sources, which structures are influenced by the enzymatic control of the precursor organisms. All of these compounds, which can provide clear evidences of its sources or information about oceanographic conditions, are called biological markers or biomarkers. The present work put out an analytic method to identify and quantify biomarkers like aliphatic hydrocarbons, PAHs, sterols and alkenones with only one lipidic extraction. This method was evaluated by several analytic criteria and validated by reference material and by interlaboratory comparison study. The method was used to analyze a marine sediment core from Cabo Frio. The alkenones quantification in this core allowed not only appreciate changes in the sea surface temperature (SST) along the years and correlate them with changes in the upwelling, but also verify how the other biomarkers responded to SST changes.

O destino de grande parte da matéria orgânica presente nos oceanos é o sedimento marinho. Essa matéria orgânica, que vai sendo armazenada ao longo dos anos, produz uma reserva única de informações sobre os processos biogeoquímicos ocorridos no passado e como esses processos responderam às mudanças ambientais. Certas moléculas orgânicas são sintetizadas apenas por organismos marinhos ou somente por plantas superiores terrestres. A abundância relativa desses compostos em sedimentos marinhos pode ser usada para determinar a contribuição de matéria orgânica terrestre ou marinha que foi depositada. Outros compostos, cujas fontes naturais são raras ou inexistem, encontrados em sedimentos, refletem a influência antrópica no meio. Há ainda compostos, com origem biológica especifica, cujas estruturas são influenciadas pelo controle enzimático dos organismos que os produzem, que são influenciados pelo meio. Esses compostos, cuja presença pode fornecer evidências inequívocas da sua fonte ou informações sobre condições oceanográficas recebem o nome de marcadores biológicos e são comumentemente abreviados como biomarcadores. Esse trabalho produziu uma metodologia analítica para identificação e quantificação de biomarcadores como os hidrocarbonetos alifáticos, hidrocarbonetos policíclicos aromáticos, esteróis e alquenonas através de uma única extração lipídica. Essa metodologia foi avaliada por diversos critérios analíticos e validada através de materiais de referência e de exercícios de comparação entre laboratórios. A metodologia foi aplicada em um testemunho de sedimento marinho obtido em Cabo Frio. A quantificação das alquenonas nas amostras do testemunho permitiu estimar a variação da temperatura da superfície oceânica ao longo dos anos e correlacioná-la com variações na intensidade da ressurgência, além de permitir verificar como os demais biomarcadores variaram em função da variação da temperatura do meio onde foram sintetizados. / The fate of most organic matter in the oceans is the marine sediment. This preserved organic matter became an unique reservoir of information about the operation of biogeochemical processes in the geological past, and how these processes responded to environmental changes. Some molecules are only synthesized by sea organisms, others only by higher plants. The relative abundance among these compounds in sea sediments can be used to determine the source of the organic matter. Other organic compounds, without natural sources, are an indicative of anthropogenic influence. The marine sediment also can accumulate compounds with the specific biological sources, which structures are influenced by the enzymatic control of the precursor organisms. All of these compounds, which can provide clear evidences of its sources or information about oceanographic conditions, are called biological markers or biomarkers. The present work put out an analytic method to identify and quantify biomarkers like aliphatic hydrocarbons, PAHs, sterols and alkenones with only one lipidic extraction. This method was evaluated by several analytic criteria and validated by reference material and by interlaboratory comparison study. The method was used to analyze a marine sediment core from Cabo Frio. The alkenones quantification in this core allowed not only appreciate changes in the sea surface temperature (SST) along the years and correlate them with changes in the upwelling, but also verify how the other biomarkers responded to SST changes.

Les alcénones sont largement utilisées comme proxys pour estimer des températures d’eaux de surface océanique ou des pressions partielles de CO2 (pCO2) dans des périodes anciennes. Dans les océans actuels, ces cétones à longues chaînes carbonées sont essentiellement produites par les coccolithophoridés Emiliania huxleyi et Gephyrocapsa oceanica. Il existe toutefois un écart temporel important entre le premier enregistrement sédimentaire des alcénones au Crétacé (~120 Ma) et la première apparition des producteurs actuels (< 2 Ma). Il apparaît donc essentiel d’identifier les producteurs anciens d’alcénones afin d’assurer la fiabilité des proxys environnementaux basés sur ces biomarqueurs pour les périodes préquaternaires. Cette thèse présente trois cas d’étude correspondant à des périodes clés de l’évolution de la famille des Noëlaerhabdaceae, qui comprend les ancêtres cénozoïques des producteurs actuels d’alcénones. La comparaison entre le contenu en alcénones (distribution et concentrations) et les abondances relatives et absolues des différentes espèces de Noëlaerhabdaceae dans des sédiments marins datant de l’Eocène-Oligocène (35-31 Ma), del’Oligocène-Miocène (25-16 Ma) et du Pliocène supérieur (3,6-2,6 Ma) montre que,contrairement aux hypothèses précédentes, Reticulofenestra n’était pas le seul genre responsable de la production d’alcénones au Cénozoïque. Les résultats démontrent également qu’il est essentiel d’identifier avec précision les producteurs et la taille de leur cellule pour les estimations de pCO2. Au contraire, l’identification formelle des producteurs ne semble pas indispensable pour obtenir des estimations de températures cohérentes. / Alkenones have been widely used as proxies for the reconstruction of sea surface temperatures and of partial pressure of CO2 (pCO2) in ancient periods. In modern oceans, these long-chain ketones are mainly produced by the coccolithophores Emiliania huxleyi and Gephyrocapsa oceanica. However, there is a huge gap between the first record of alkenonesin the Cretaceous (~120 Ma) and the first occurrence of the modern alkenone producers (< 2Ma). Thus, it seems crucial to identify ancient alkenone producers to ensure the applicability of environmental proxies based on these biomarkers in pre-Quaternary sediments. In this PhD thesis, three case studies are considered corresponding to key periods in the evolution history of the Noelaerhabdaceae family, which includes the Cenozoic ancestors of modern alkenone producers. The comparison between alkenone contents (distribution and concentrations) andNoelaerhabdaceae species-specific relative and absolute abundances in marine sedimentsdating back to the Eocene-Oligocene (35-31 Ma), the Oligocene-Miocene (25-16 Ma) and thelate Pliocene (3.6-2.6 Ma) shows that, contrary to common assumptions, Reticulofenestra was not the only genus responsible for alkenone production during the Cenozoic. Results also underscore the importance of a careful identification of alkenone producers and of their cellsize for pCO2 reconstructions for pre-Quaternary periods. On the contrary, the identificationof producers does not seem essential to obtain consistent paleo-temperature estimates.

Reconstructing past sea surface temperature conditions is valuable to observe and evaluate the climate of the past. In the SW Atlantic, so far, few studies have exanimated the applicability of paleotemperature equations, which may reflect in fewer reliable SST estimates. This study aimed to evaluate two marine proxies for SST reconstructions: the alkenones unsaturation index (UK\'37) and the ratio Mg/Ca in different planktonic foraminifera species and size fractions (G. ruber pink; G. ruber white senso stricto and senso lato; between 250 - 300 µm and 300 - 355 &#956;m; G. truncatulinoides (d) crusted and non-crusted forms, between 380 - 620 &#956;m; and G. inflata 300 - 425 &#956;m). The samples were collected in the shelf break of South Brazilian Bight (SBB, 22 °S to 27 °S). The proxies were converted into SSTs and then compared to modern SSTs from the World Ocean Atlas and satellite images. The first chapter describes the UK\'37 signals and the applicability of three different paleotemperature equations, and the second chapter describes the Mg/Ca a proxy for past SSTs and water mass conditions after applying the most used paleotemperature equations for the ratio Mg/Ca. The UK\'37 seems to record mostly autumn conditions at 0m, and the most recent Bayspline equation results into more similar temperature averages when compared to modern annual SSTs (p-value of 0.81, n = 47, &#916;SST of -0.03°C &#177; 0.27), while the most used linear equations result into SSTs similar to autumn conditions. In subtropical regions with low-temperature variations (&#8764;4°C), the function UK\'37 versus SSTs works in an exponential relation, and they are related to seasonal temperatures. For the Mg/Ca in planktonic foraminifera species, the Mg/Ca-inferred temperatures agree well with modern ocean temperatures. Our data suggest that in different size fractions the tested species respond differently to the most used species-specific and general species paleotemperature equations. All the upper water column species agree well with temperatures at 0-meter depth. The G. ruber (p) responds well to the SS equation, where the smallest and the largest size results into annual and autumn estimates, respectively (p-value of 0.81 and 0.71, n = 23); the smallest size of G. ruber (w) s.s. provides summer estimates applying the GE equation (p-value of 0.21, n = 7), while the largest size provides annual estimates (p-value of 0.86, n = 13). The G. ruber (w) s.l. has significant averages when compared the largest size with autumn and summer conditions (p-value of 0.21 for both, n = 16); the deep-dwelling species G. inflata and the G. truncatulinoides (d) crusted form reflect the uplift of the SACW, calcifying at 10 and 20 m depth (p-value of 0.89, n = 10 and p-value of 0.06, n = 14, respectively), while the G. truncatulinoides (d) non-crusted form records annual temperature in deep water layers conditions (p-value of 0.06, n = 16). This is the first study to report Mg/Ca ratios in surface-dwelling and deep-dwelling planktonic foraminifera tests obtained in core-top samples at the SBB. This validation will inform the reconstruction of past environmental conditions of SW Atlantic, especially in the SBB. / As reconstruções das condições da temperatura superficial do mar são importantes para avaliar o clima do passado da Terra. No Atlântico SE, no entanto, poucos estudos avaliaram a aplicabilidade das equações de conversão dos indicadores geoquímicos para temperatura, o que pode resultar em estimativas de paleotemperatura de menor acurácia. Este estudo avaliou dois indicadores marinhos de paleotemperatura: o índice de insaturação de alquenonas (UK\'37), e a razão Mg/Ca em testas de foraminíferos planctônicos de diferentes espécies e frações de tamanho (G. ruber pink; G. ruber white senso stricto e senso lato; entre 250 - 300 &#956;m e 300 - 355 &#956;m; G. truncatulinoides (d) encrustadas e não-encrustadas, entre 380 - 620 &#956;m; e G. inflata 300 - 425 &#956;m). As amostras são provenientes da plataforma externa e quebra da plataforma do Embaiamento de São Paulo (22°S a 27°S). Os indicadores foram transformados em TSM e então comparados com as temperaturas obtidas por meio do World Ocean Atlas e de imagens de satélite. O primeiro capítulo apresenta os dados de UK\'37 e a aplicabilidade de três equações de paleotemperatura. O segundo capítulo apresenta dados da razão Mg/Ca como indicador de TSM e condições de massa d\'água após a aplicação das equações de conversão. O UK\'37 apresenta influência do outono em 0 m de profundidade em seus registros, e a mais recente equação Bayspline resulta em médias de TSM mais similares com as condições atuais, principalmente quando comparado com a média anual de TSM (p-valor de 0.81, n = 47, &#916;SST de -0.03°C &#177; 0.27), já as equações lineares mais conhecidas resultam em TSM mais parecidas com condições de outono. No geral, em regiões com pouca variação de TSM (&#8764;1.5 °C), o UK\'37 responde em uma relação exponencial com a temperatura. A razão Mg/Ca em testas de foraminíferos planctônicos, quando convertidas em TSM, resultam em médias similares com as condições atuais de temperatura. Os nossos dados sugerem que as equações específicas para cada espécie (SS) e as equações gerais (GE) resultam em diferentes médias de TSM para cada espécie/fração de tamanho. Todas as espécies de superfície respondem bem com as temperaturas em 0 metros de profundidade. A G. ruber (p) responde bem à equação SS, onde a menor e a maior fração de tamanho resulta em médias similares às TSM anuais e de outono, respectivamente (p-valor de 0.81 e 0.71, n = 23); a menor fração de tamanho da espécie G. ruber (w) s.s. resulta em médias similares às TSM de verão com a equação GE (p-valor de 0.21, n = 7), enquanto a maior fração de tamanho resulta em TSM anual (p-valor de 0.86, n = 13). A maior fração de tamanho da espécie G. ruber (w) s.l. resulta em médias significativas quando comparadas com TSM de outono e de verão (p-valor de 0.21 para ambas, n = 16). Os registros geoquímicos das espécies de subsuperfície, como a G. inflata e a G. truncatulinoides (d) encrustada registram a subida da ACAS para a superfície na área de estudo, calcificando em 10 e 20 metros de profundidade, respectivamente (p-valor de 0.89, n = 10 e de 0.06, n = 14, respectivamente), enquanto a G. truncatulinoides (d) não-encrustada aparenta registrar as condições anuais de temperatura em profundidades mais próximas da ACAS, com médias um pouco mais elevadas que as duas espécies de subsuperfície (p-valor de 0.06, n = 16). Este é o primeiro estudo que relata as razões Mg/Ca em diferentes espécies de foraminíferos planctônicos no ESP. Esta validação auxiliará a aprimorar futuras estimações de TSM com este indicador.

This thesis presents investigations on sediments from two African lakes which have been recording changes in their surrounding environmental and climate conditions since more than 200,000 years. Focus of this work is the time of the last Glacial and the Holocene (the last ~100,000 years before present [in the following 100 kyr BP]). One important precondition for this kind of research is a good understanding of the present ecosystems in and around the lakes and of the sediment formation under modern climate conditions. Both studies therefore include investigations on the modern environment (including organisms, soils, rocks, lake water and sediments). A 90 m long sediment sequence was investigated from Lake Tswaing (north-eastern South Africa) using geochemical analyses. These investigations document alternating periods of high detrital input and low (especially autochthonous) organic matter content and periods of low detrital input, carbonatic or evaporitic sedimentation and high autochthonous organic matter content. These alternations are interpreted as changes between relatively humid and arid conditions, respectively. Before c. 75 kyr BP, they seem to follow changes in local insolation whereas afterwards they appear to be acyclic and are probably caused by changes in ocean circulation and/or in the mean position of the Inter-Tropical Convergence Zone (ITCZ). Today, these factors have main influence on precipitation in this area where rainfall occurs almost exclusively during austral summer. All modern organisms were analysed for their biomarker and bulk organic and compound-specific stable carbon isotope composition. The same investigations on sediments from the modern lake floor document the mixed input of the investigated individual organisms and reveal additional influences by methanotrophic bacteria. A comparison of modern sediment characteristics with those of sediments covering the time 14 to 2 kyr BP shows changes in the productivity of the lake and the surrounding vegetation which are best explained by changes in hydrology. More humid conditions are indicated for times older than 10 kyr BP and younger than 7.5 kyr BP, whereas arid conditions prevailed in between. These observations agree with the results from sediment composition and indications from other climate archives nearby. The second lake study deals with Lake Challa, a small, deep crater lake on the foot of Mount Kilimanjaro. In this lake form mm-scale laminated sediments which were analyses with micro-XRF scanning for changes in the element composition. By comparing these results with investigations on thin sections, results from ongoing sediment trap studies, meteorological data, and investigations on the surrounding rocks and soils, I develop a model for seasonal variability in the limnology and sedimentation of Lake Challa. The lake appears to be stratified during the warm rain seasons (October – December and March – May) during which detrital material is delivered to the lake and carbonates precipitate. On the lake floor forms a dark lamina with high contents of Fe and Ti and high Ca/Al and low Mn/Fe ratios. Diatoms bloom during the cool and windy season (June – September) when mixing down to c. 60 m depth provides easily bio-available nutrients. Contemporaneously, Fe and Mn-oxides are precipitating which cause high Mn/Fe ratios in the light diatom-rich laminae of the sediments. Trends in the Mn/Fe ratio of the sediments are interpreted to reflect changes in the intensity or duration of seasonal mixing in Lake Challa. This interpretation is supported by parallel changes in the organic matter and biogenic silica content observed in the 22 m long profile recovered from Lake Challa. This covers the time of the last 25 kyr BP. It documents a transition around 16 kyr BP from relatively well-mixed conditions with high detrital input during glacial times to stronger stratified conditions which are probably related to increasing lake levels in Challa and generally more humid conditions in East Africa. Intensified mixing is recorded for the time of the Younger Dryas and the period between 11.4 and 10.7 kyr BP. For these periods, reduced intensity of the SW monsoon and intensified NE monsoon are reported from archives of the Indian-Asian Monsoon region, arguing for the latter as a probable source for wind mixing in Lake Challa. This connection is probably also responsible for contemporaneous events in the Mn/Fe ratios of the Lake Challa sediments and in other records of northern hemisphere monsoon intensity during the Holocene and underlines the close interaction of global low latitude atmospheric circulation. / In dieser Arbeit werden Ergebnisse von Untersuchungen an den Sedimenten zweier afrikanischer Seen vorgestellt, die ein Archiv für Klimaveränderungen über einen Zeitraum von mehr als 200.000 Jahren darstellen. Der Schwerpunkt liegt in dieser Arbeit auf dem letzten Glazial und dem Holozän (ca. 100.000 Jahre vor heute [nachfolgend als 100 kyr BP bezeichnet] bis heute). Grundlegende Voraussetzung für solche Studien ist ein gutes Verständnis der Ökosysteme in und um den See, sowie des gegenwärtigen Sedimentationsgeschehens. Deswegen beinhalten beide Seestudien Untersuchungen der heutigen Organismen, Böden, Gesteine, Wasserchemie und Sedimentablagerungen. Im Tswaing-See im nordöstlichen Südafrika wurden anhand eines 90 m langen Sedimentprofils Studien zur Sedimentzusammensetzung und Untersuchungen der Zusammensetzung und Qualität des organischen Materials durchgeführt. Sie zeigen einen Wechsel zwischen Phasen hohen detritischen Eintrags, während derer v.a. kaum autochthones organisches Material im See erhalten blieb, mit Phasen geringen Eintrags und dafür karbonatischer oder evaporitischer Sedimentation, die hohe Gehalte v.a. autochthonen organischen Materials aufweisen. Diese Phasen werden als relativ feuchte bzw. trockene Perioden interpretiert und folgen bis vor ca. 75 kyr BP Schwankungen der lokalen solaren Einstrahlung. Dieser Einfluss nimmt nach 75 kyr BP ab und azyklische feuchte Phasen werden beobachtet. Mögliche Ursachen sind Veränderungen in der ozeanischen Zirkulation und Verschiebungen in der Lage der Innertropischen Konvergenzzone (ITCZ); beides sind auch heute Haupteinflussfaktoren auf die Niederschläge in der Region. Die heute lebenden Organismen des Tswaing-Kraters wurden mittels Analysen der Biomarkerzusammensetzung und der Kohlenstoffisotopie charakterisiert und ihr Einfluss auf die heutigen Seeablagerungen untersucht. Dabei konnten zusätzlich Indikatoren für die Aktivität methanotropher Bakterien nachgewiesen werden. Der Vergleich heutiger Sedimente mit denen des Zeitraumes 14 bis 2 kyr BP zeigt deutliche Veränderungen sowohl in der Zusammensetzung, als auch in der Kohlenstoffisotopie der Biomarker, die mit Veränderungen in der Hydrologie erklärt werden können. Die gefundenen Hinweise auf feuchtere Bedingungen im Zeitraum älter als 10 kyr BP, für trockenere Verhältnissen zwischen 10 und 7.5 kyr BP und für die nachfolgende Wiederzunahme an Feuchtigkeit werden durch die sedimentologischen Ergebnisse unterstützt. Objekt der zweiten Seestudie ist der Challa-See am Fuß des Kilimanjaro. Hier werden heute im mm-Maßstab laminierte Sedimente gebildet, die mit Mikro-XRF-scanning auf Veränderungen in der Elementzusammensetzung untersucht wurden. Zusammen mit Untersuchungen der Mikrofazies und im Vergleich mit ersten Ergebnissen noch laufender Sedimentfallenstudien, mit meteorologischen Daten und Analysen des Umgebungsgesteins werden die saisonalen Veränderungen in der Temperaturverteilung, der Durchmischungstiefe, dem detritischen Eintrag und der Bioproduktivität des Sees in den Sedimenten nachvollziehbar. Der See ist in den feucht-warmen Perioden von Oktober bis Dezember und von März bis Mai stratifiziert. Während dieser Zeit erfolgt der Eintrag detritischen Materials und Kalziumkarbonat fällt aus; eine dunkle Lage mit hohen Gehalten an Fe und Ti und mit hohen Ca/Al- und niedrigen Mn/Fe-Verhältnissen bildet sich am Boden des Sees. Diatomeen blühen während der kühlen, windigen Periode von Juni bis September, wenn die Durchmischung bis auf etwa 60 m Tiefe Nährstoffe verfügbar macht. Die Ausfällung von Fe- und Mn-oxiden sorgt für hohe Mn/Fe-Verhältnisse; es bildet sich eine helle Lage auf dem Sediment. Trends im Mn/Fe-Verhältnis werden als Signal für Veränderungen in der Intensität oder Dauer der saisonalen Durchmischung interpretiert. Dies wird unterstützt durch parallele Trends im Gehalt an organischem Material und an biogenem Silizium, wie durch Analysen an einem 22 m langen Bohrkern gezeigt werden kann. Nach gut durchmischten und von erhöhtem Eintrag von außen geprägten Verhältnissen während des letzten Glazials erfolgt gegen 16 kyr BP ein Übergang zu stärker stratifizierten Bedingungen. Diese korrespondieren mit einem steigenden Seespiegel und verbreiteten Hinweisen auf feuchte Bedingungen im tropischen Ostafrika. Stärkere Durchmischung herrschte während der Jüngeren Dryas und von 11.4 bis 10.7 kyr BP. Diese Perioden entsprechen Zeiten verringerter Südwest- und vermutlich verstärkter Nordostmonsunintensität im Bereich des Indisch-Asiatischen Monsuns und spiegeln eine global beobachtete südliche Verschiebung der ITCZ wider. Nach einer kurzen stabilen, feuchten Phase im frühen Holozän nimmt die Durchmischung des Sees im Verlauf des Holozän wieder zu. Abrupte Ereignisse während des Holozän scheinen im Challa-See zeitgleich mit Veränderungen der Monsunintensität der Nordhemisphäre aufzutreten und bezeugen die starke klimatische Kopplung der niederen Breiten in globalem Maßstab.

Tandis que la variabilité climatique à long terme du Quaternaire terminal (oscillations glaciaire/interglaciaire) est relativement bien appréhendée aujourd’hui, l'origine et la modalité des variations climatiques haute-fréquence séculaires à millénaires, depuis la très haute fréquence des cycles de Dansgaard-Oeschger (D/O) jusqu'à la plus grande périodicité des événements d'Heinrich, restent toujours matière à débat. Parmi les éléments encore équivoques se trouvent notamment les modalités de transferts de chaleur méridiens et latitudinaux. A ce titre, la connexion hydrologique entre l’Atlantique et la Méditerranée apparaît comme un exemple d’étude particulièrement approprié vu qu’elle illustre le couplage de phénomènes jouant selon un double gradient Est-Ouest et Nord-Sud, reliant ainsi processus subtropicaux et nord atlantiques. Nous avons ainsi ciblé nos analyses sur des séquences prélevées autour du détroit de Gibraltar, avec pour objectif d’étendre les connaissances spatiales et temporelles de la variabilité climatique haute fréquence des derniers 50 000 ans dans le secteur de l’Atlantique Est subtropical et de la Méditerranée occidentale. La méthodologie de cette thèse est ainsi basée sur une comparaison multi-proxies qui inclut des analyses micropaléontologiques (dinokystes et foraminifères planctoniques) et géochimiques (isotopes stables et alkénones). Nous avons ainsi pu tester la cohérence des changements hydrologiques de surface inter- et intra-bassins et tenter de caractériser la migration des fronts hydrologiques associés. Grâce aux sites des marges marocaine et portugaise, notamment, nous avons pu vérifier l’impact des cycles de D/O sur la variabilité de l’intensité des cellules d’upwelling côtières dans ce secteur et sur la dynamique de la veine d’eau méditerranéenne profonde (MOW), couplant signaux des masses d’eau superficielles (température, salinité et productivité) aux paléo-intensités de la MOW. / While the long-term climatic variability of the Quaternary is relatively well understood today, the causes and processes at the origin of the rapid and brutal climatic variability that characterized the last glacial period (Dansgaard-Oeschger cycles), including meridional and latitudinal heat transfer mechanisms, are still subject to debate. As such, studying the hydrological connection between the Atlantic and the Mediterranean Sea appears particularly appropriate since it illustrates the coupling acting on a double East-West and North-South gradient. It furthermore links subtropical processes and North Atlantic ones. We focused our analysis on sedimentary sequences retrieved around the Strait of Gibraltar, in order to extend the spatial and temporal knowledges about the impact of the high frequency climatic variability of the last 50 000 years in the sector of the eastern subtropical Atlantic and of the western Mediterranean Sea. The methodology of this thesis is based on a multi-proxy compilation coupling micropaleontological (dinocysts and planktonic foraminifera) and geochemical (stable isotopes and alkenones) approaches. We have tested the consistency of the sea-surface paleohydrological changes at inter-and intra-basins scales and tried to characterize the associated migration of the hydrological fronts. Sites of the Portuguese and Moroccan margins, in particular, allowed us to document the impact of the D/O cycles on the intensity of coastal upwelling cells as well as on the dynamics of the MOW, by coupling sea surface signals (temperature, salinity and productivity) to paleointensity of the MOW.

Les alcénones constituent une classe de cétones insaturées à longue chaîne (C35 à C41)synthétisées par un nombre limité d’haptophytes. La proportion des alcènones en C37 di et triinsaturéesvarie en fonction de la température de croissance de l’haptophyte. A partir de cette caractéristique et de leur ubiquité dans l’environnement marin, un indice nommé '37U K =[C37 :2] / ([C37 :2 + C37 :3]) est utilisé depuis la fin des années 1980s comme paléomarqueur des températures des eaux de surface.Des processus de dégradation biotique et abiotique sélectifs, jusqu’alors partiellement ignorés,peuvent entraîner des biais significatifs (du fait de la perte préférentielle des alcénones les plus insaturées) dans les valeurs de paléotempératures estimées à partir de l’ '37U K . Ce travail a été entrepris dans le but d'étudier l'impact de ces processus diagénétiques sur les alcénones et d'évaluer leur importance dans l'environnement marin.Durant la première partie de ce travail, nous avons isolé et identifié diverses souches bactériennes à partir de cultures d’Emiliania huxleyi, que nous avons testées pour leur capacité à dégrader les alcénones. La souche Dietzia maris s'est révélée capable de dégrader sélectivement les alcénones. Cette dégradation sélective fait intervenir une époxydation initiale des doubles liaisons des alcénones, qui est vraisemblablement induite par une monoxygénase ayant une plus grande affinité pour la double liaison en position w29 et peut conduire à une augmentation des valeurs de l' '37U K de l’ordre de +0,10 (soit une surestimation des températures de +3°C).L'impact de ces processus de dégradation (biotique et abiotique) in situ s'est révélé plus oumoins significatif selon les zones géographiques considérées. En mer Méditerranée,l'augmentation des valeurs de l' '37U K (0,43 à 0,55) s'explique essentiellement par une forte autoxydation des alcénones lors de leur sédimentation. La détection d'alcénones stéréomutées à la surface du sédiment nous a permis d'estimer que les processus de stéréomutatio npouvaient entraîner un biais dans les valeurs de l' '37U K de +0,05 dans cette région. En Alaskaainsi que dans le Pacifique équatorial, les biais observés résultent essentiellement d’une dégradation bactérienne sélective des alcénones (+0,7 à +2,4°C et +2°C, respectivement).Lors de nos analyses de matériel particulaire provenant de l’océan Pacifique équatorial, nos observations ont mis en évidence une relation entre l’état de photo-oxydation des cellules phytoplanctoniques sénescentes et l’état physiologique des bactéries qui leur sont associées.Un transfert d’oxygène singulet (1O2) des phytodétritus aux bactéries entraînerait un déclin important de la croissance bactérienne et limiterait ainsi considérablement la biodégradation.Dans notre étude, ce transfert d’1O2 s’est révélé plus efficace dans les particules en suspension(forte photo-oxydation des bactéries) que dans les particules prélevées par trappes (forte biodégradation du phytodétritus). Cette différence s’expliquerait par l’abondance de particules riches en silice dans les particules prélevées par trappes (dominées par des agglomérats de diatomées) dont le caractère polaire réduirait la durée de vie de l’1O2.Nos résultats confirment que les processus de (i) dégradation bactérienne sélective, (ii)d'autoxydation et (iii) de stéréomutation peuvent introduire des bais significatifs dans les reconstructions de paléotempératures et des moyens de corriger les biais résultant de cette diagenèse ont été proposés afin d'améliorer les reconstructions de paléotempératures basées sur cet outil. / Alkenones constitute a class of long-chain unsaturated ketones (C35 to C41) synthesized by alimited number of haptophytes. The proportion of C37 di- and tri-unsaturated alkenones varies according to the growth temperature of the haptophytes. From this characteristic and theubiquity of alkenones in the marine environment, an index named '37U K = [C37: 2] / ([C37: 2 + C37:3]) is used since the late 1980s as paleomarker of sea surface temperatures. Selective biotic and abiotic degradation processes, previously ignored in the literature, canlead to significant biases (due to the preferential loss of the more unsaturated alkenones) in paleotemperature values estimated from the '37U K . This work was undertaken to estimate theimpact of diagenetic processes on alkenones in the marine environment.During the first part of this work, we isolated and identified various bacterial strains from cultures of Emiliania huxleyi, which were tested for their ability to degrade alkenones. Thestrain Dietzia maris sp. S1 appeared to be able to degrade selectively di- and tri-unsaturatedalkenones. This selective degradation involves an initial epoxidation of alkenone doublebonds, which is probably induced by a monooxygenase showing a greater affinity for the w29double bond and leads to increases of the '37U K values ranging from +0.05 to +0.10 units(corresponding to an overestimation of temperatures of 1.5 - 3°C).The impact of these biotic and abiotic degradation processes in situ was more or lesssignificant depending on the area considered. In Mediterranean Sea, increasing values of '37U Kwith depth (0.43 to 0.55) seemed to mainly result from an intense autoxidation of alkenones.The detection of stereomutated alkenones in surface sediments also attested to the importanceof these processes in this region (increased in '37U K values of +0.05 units). In contrast, in Alaska and Equatorial Pacific, the biases observed (+0.7 to +2.4°C and +2°C, respectively) appeared to be mainly induced by selective bacterial degradation of alkenones.Analyses of particulate matter from the Equatorial Pacific Ocean, revealed a relationshipbetween the state of photo-oxidation of senescent phytoplankton cells and the physiologicalstate of associated bacteria. A transfer of singlet oxygen (1O2) from phytodetritus to thebacteria may induce damages in bacteria and thus significantly limit biodegradation. This transfer of 1O2 appeared to be more effective in suspended particles (high photo-oxidation ofbacteria and preservation of phytodetritus) than in the sinking particles (weak photo-oxidationof bacteria and high biodegradation of phytodetritus). These differences were attributed to theabundance of particles rich in silica in sinking particles (dominated by agglomerates ofdiatoms), whose the polar character could reduce lifetime of 1O2.Our results confirm that the process of (i) selective bacterial degradation, (ii) autoxidation and(iii) stereomutation may introduce significant biases in the reconstruction ofpaleotemperatures. Some tools were proposed to correct some of these biases and thus toimprove the paleotemperature reconstructions based on alkenones