Lake deposits are widespread throughout the Phanerozoic rock record and have long intrigued geologists and paleobiologists in search of natural resources or fossil biota. Low-energy lacustrine depositional environments, characterized by relatively rapid sediment influx rates and shallow zones of bioturbation, likewise produce highly-resolved archives of climate and ecosystems evolution. This dissertation describes four studies that use lake sediments for Quaternary environmental analysis. In East Africa, many decades of prior study provided the critical framework necessary for in-depth paleoenvironmental research at Lake Tanganyika (3° - 9°S). Seismic stratigraphic analysis integrated with radiocarbon-dated sediment cores from the Kalya horst and platform document a dramatic lake level lowstand prior to ~106 ka and a minor, short-lived regression during the Last Glacial Maximum (32 - 14 ka). Paleobathymetric maps reveal that Lake Tanganyika remains a large, connected water body even during episodes of extreme drought, which has implications for local and regional fauna. Over shorter timescales, geochronological, taphonomic and sedimentological analyses of shell beds around Kigoma (central Lake Tanganyika) document three distinct facies-types that are time-averaged over the latest Holocene. Lake level fluctuations associated with the termination of the Little Ice Age (~ 16th century CE) and subsequent encrustation played a key role in shell bed formation and persistence along high-energy littoral platforms, which has implications for structuring specialized communities of benthic fauna. In central South America (18° - 22°S), we studied the limnogeology of small lakes in the Puna and the Pantanal. Analyses of these sites were undertaken to: 1) ascertain how the lakes act as depositional basins; 2) assess sedimentation rates; and 3) construct limnogeological databases to guide future interpretations of ancient sediment cores. At Laguna de los Pozuelos (Argentine Puna), linear sedimentation rates approach 0.14 cm*y⁻¹ in the playa-lake center, and litho- and organo-facies development are dominantly controlled by basin hydrology, climate and biological feedbacks (both nutrient cycling and bioturbation) from waterbirds. At Lagoas Gaíva, Mandioré and Vermelha (Brazilian Pantanal), short-lived radioisotopes indicate uninterrupted depositional rates of 0.11 - 0.24 cm*y⁻¹, and hydrochemical and depositional patterns respond sensitively to changes in the seasonal flooding cycle of the Upper Paraguay River.

In this study diatom distribution within the lower Save River, Mozambique, has been identified from surface sediments, surface water, mangrove cortex and buried sediments. Sandy units, bracketing a geographically extensive clay layer, have been dated with optical stimulated luminescence (OSL). Diatom analysis has been used to interpret the spatial salinity gradient and to discuss taphonomic processes within the delta. Previously, one study has been performed in the investigated area and it is of great importance to continue to identify diatom distributions since siliceous microfossils are widely used for paleoenvironmental research. Two diatom taxa, which were not possible to classify to species level have been identified; Cyclotella sp. and Diploneis sp. It is suggested that these represent species not earlier described; however they are assigned a brackish water affinity. Diatom analysis from surface water, surface sediments and mangrove cortex indicate a transition from ocean water to a dominance of freshwater taxa c. 10 km upstream the delta front. Further, ratios between marine/brackish taxa for samples from surface water and surface sediments do not correspond. It is therefore suggested that diatoms in surface sediments underestimate prevailing salinity conditions in water. In the investigated area extensive taphonomic processes seem to have large impact on diatom frustules in sediments and may bias interpretations. Therefore it is recommended to carefully investigate geology, geomorphology and vegetation before diatom analysis is applied in studies of delta paleoenvironments.

Long-term palaeo-climatic conditions have primarily been interpreted from ocean marine sediments and ice cores. Few middle and low latitude continental records exist that provide insight into continental response to climate change over time. This research offers new chronologies on a variety of low latitude continental deposits from the Southern High Plains, and demonstrates their importance as palaeo-environmental archives. These chronologies extend the existing Southern High Plains palaeo-environmental record from the historic period to the late-middle Pleistocene, and provide an important basis from which to examine landscape response to late Quaternary climate change. This study demonstrates the applicability of optical dating procedures to well-bleached sedimentary features, such as lunettes, lacustrine material, tufa, and coversands. The precision and accuracy of the technique permits the detection of historic depositional events, whilst the range of the dating technique extended the chronology to the middle-late Pleistocene. The physical isolation of the Southern High Plains from its surrounding areas for the last 1.6 Ma has preserved a record of past climatic fluctuations within the aeolian and fluvio-lacustrine sediments. This research has demonstrated that the Southern High Plains landscape is sensitive to periods of less effective moisture, causing reactivation during historic drought periods (e.g. 1930s "Dust Bowl" event). Coversands and small playa lunettes were active during glacial and interglacials. This suggests that these features are sensitive to smaller scale climatic fluctuations that result in reduced effective moisture for the region during both glacial and interglacial periods. Large lake lunettes were inactive during the Wisconsin glacial. During this same period, active lacustrine and tufa deposition occurred; this offers evidence of greater effective moisture for the Southern High Plains, which resulted in regional recharge. The record of climate change preserved in the lunettes, lacustrine material, tufa, and coversands has provided insight into the response of this dynamic landscape to climatic fluctuations and has been employed for the reconstruction of the palaeo- environmental history of the Southern High Plains. An understanding of landscape response is important in light of the future of the Southern High Plains environment as global temperatures increase, and is critical to a complete evaluation of continental response to climatic change.

A detailed record of the Late Holocene sea level rise and landscape evolution that has taken place on the Georgia coast is contained within the sedimentary stratigraphy of its salt marsh depositional basins. Global relative sea level (RSL) has risen during the Late Holocene, and the rate of rise has accelerated during the Anthropocene. Jones Narrows marsh stratigraphy and radiocarbon analysis indicate increasing rates of RSL rise for the late Holocene on the Northern Atlantic Coast of Georgia, while FPXRF analysis of the marsh sediments facilitates a chemostratigraphic study of Jones Narrows salt marsh deposition and landscape evolution. Sedimentation and hydrology at the site have been heavily influenced by recent local anthropogenic impacts, which are examined through stratigraphic and spatial methods.

Lakes Magadi (Kenya) and Manyara (Tanzania) occupy closed basins in the southern Gregory Rift valley. Water in these lakes is presently shallow and saline, testifying to the dominance of evaporation (E) over precipitation (P). Past changes in the P: E ratio, and hence in palaeoclimate, can be reconstructed from evidence of the former extent of these lakes. Lake-level fluctuations engender marked variation in water chemistry, and consequently on the composition of the limnological biota. One approach is to examine the sedimentary record of diatoms (unicellular algae), which are excellent indicators of water chemistry and relative water depth, and whose modem distribution is sufficiently well known to allow the quantitative reconstruction of chemical parameters. Diatom analysis of 116 samples from a series of radiometrically dated (14C and U/Ib) sediment cores has revealed significant changes amongst the diatom assemblages during the Late Quaternary. Conductivity and pH have been estimated from the fossil samples by transfer functions (Gasse unpublished, Gasse 1986b). However, the interpretation of fossil diatom assemblages is often problematical in hypersaline environments. Difficulties arise as a result of the operation of taphonomic and diagenetic processes which can severely alter the composition of the diatom assemblagesfr om the ambient population at the time of deposition. Probably the most important factor responsible for assemblage diagenesis in saline lakes is silica dissolution, and this is explored further by a series of laboratory experiments. Results indicate that silica dissolution acts differentially between species, by removing the smaller, more delicate taxa first, and causing the relative enrichment of large robust forms in the fossil samples. A similar dissolution gradient may be reflected in modem samples studied near hot springs at Magadi. Differential dissolution is potentially an important source of error in palaeoenvironmental reconstructions, but, with the outcome of these experiments, it has been possible to assess the extent to which the dissolution process may have shaped the diatom records from Magadi and Manyara. The bulk of the palaeolimnological evidence is focussed upon two periods, 30,000-20,000 BP and 12,700-9,500 BP. The earlier period is most clearly dated in the core from Manyara, where the diatom record suggests the development of an intermediate level lake between c. 27,500 BP and c. 26,000 BP. This is a more complete representation of the same lake phase found in earlier studies from Manyara by Holdship (1976) based on diatoms, and by Casanova (1986a) on stromatolites 20M above the present lake. This time interval may also be represented by the central portion of the Magadi cores NF1 and NF2 but here dating is more problematical. The period 12,700-9,500 BP was one of major lacustrine transgression across Africa although the fine-structure of this event is less well known. Cores NF1 and NF2 from Magadi provide a detailed register of this phase indicating a major highstand from c. 12,700-11,000 BP when the lake became deep enough to stratify and deposit laminated couplets. At c. 11,000 BP the diatoms show that salinity increased greatly from fresh-oligosaline to meso-hypersaline which was probably a consequence of lake level falling.

A baixa temperatura média anual (< 18ºC), a localização em zona de altitude elevada (> 1500 m) e a diversidade florística, bem representativa da parte sul da serra da Mantiqueira, tornam a região de Monte Verde (município de Camanducaia, sudeste do Estado de Minas Gerais), propícia para a investigação de mudanças climáticas ocorridas no Quaternário tardio, meta desta Dissertação. Para buscar esta meta, propõe-se como objetivo a análise e descrição da sucessão paleoflorística, integrada ao aporte sedimentar e às condições geoquímicas de deposição nesta região, com base de dados palinológicos, sedimentológicos (granulometria, concentração de matéria orgânica e teor e tipos de minerais pesados) e geocronológicos (datações 14C por espectrometria de aceleração de massa). A área amostrada foi a margem esquerda do Córrego dos Cadetes, afluente do rio Jaguari. Trata-se de um vale fluvial encaixado em alvéolo de relevo acidentado, onde se coletou testemunho raso (2,10m) contínuo, com equipamento vibrocorer (vibro-amostrador). Os depósitos sedimentares tertemunhados são argilo-arenosos orgânicos e turfosos. Sua análise sedimentológica demonstra a ocorrência de variações graduais e cíclicas relacionadas a mudanças no balanço entre aporte sedimentar terrígeno e biodretítico e/ou orgânico, controlado por alterações no tipo de processo deposicional, e, por extensão, na cobertura vegetal, esta possivelmente influenciada por oscilações climáticas do Quaternário Tardio. As cinco datações obtidas ficaram compreendidas no intervalo entre 20830-20370 anos 14C cal A.P. (100 cm de profundidade) e 2350?2150 anos 14C cal A.P. (10 cm). Os dados palinológicos permitem interpretar que durante todo esse período a região foi dominada por floresta, principalmente com a presença de Araucaria angustifolia, sob clima predominantemente frio e úmido, porém com possíveis oscilações de umidade. Para efeito de inferências paleoclimáticas, quatro fases principais foram identificadas, expressas a seguir em idades extrapoladas. A primeira fase corresponde ao intervalo de 17000 a 15000 anos A.P., no qual há oscilação da cobertura vegetal e aumento de erosão nas encostas, sob clima frio e úmido. Na segunda fase, de 15000 a 9000 anos A.P., detectou-se aumento de umidade acompanhado da redução do aporte trativo. A terceira fase, correspondente ao intervalo de 9000 a 8000 anos A.P., registra decréscimo na umidade e aumento da taxa de sedimentação. Nos últimos 8000 anos A.P., ocorre a manutenção da floresta de Araucaria em condições climáticas frias e úmidas. / Low annual average temperature (< 18ºC), the localization in a zone of high altitude (> 1500 m) and high floristic diversity, representative of the southern part of the Serra da Mantiqueira highlands, turn the Monte Verde region (city of Camanducaia, Southeast of the State of Minas Gerais), propitious for the inquiry of Late Quaternary climatic changes, the aim of this dissertation. The objective of the study is to analyze and describe the paleofloristic succession based on palynology, integrated with sedimentological (grain size and heavy mineral analysis), geochemical (quantification of organic matter) and geochronological (14C AMS dating) data. The sampled area is located at the left margin of the Cadetes stream, a tributary of the Jaguari River. A 2.10 m long sediment core was collected on the fluvial valley with a vibrocore equipment. The sandy-clay sediments show a high organic content and are similar in appearance to peatbog deposits. The sedimentological analysis demonstrate the occurrence of gradual and cyclic variations related to the change in incoming of terrigenous biodetrital/organic sediments, controlled by alterations in the type of depositional process, and, therefore, possibly by the vegetation cover. All these changes were possibly influenced by climatic oscillations of the Late Quaternary. The five 14C AMS dates obtained encompass the period between 20830-20370 14C cal. A.P. (100 cm of depth) and 2,350-2,150 years 14C cal. A.P. (10 cm). The palynological results indicate that in the last 20,000 years the landscape was characterized by Araucaria angustifolia forest under predominantly cold and humid climates, with minor oscillations of humidity. Four pollen phases had been identified, with extrapolated ages for paleoclimatic inferences. The first one corresponds to the interval between 17,000 and 15,000 years A.P. with oscillation of the forest cover under cold and humid climate. Between 15,000 and 9,000 years A.P., there is an increase of humidity and reduction of tractive sedimentary supply. The third interval corresponds to the period between 9,000 and 8,000 years A.P. with a decrease in humidity and increase of the sedimentation rate. In the last 8,000 years A.P. Araucaria forest was maintained under cold and humid climatic conditions, as it did during the Late Pleistocene.

Thesis advisor: James P. Morken / Platinum-catalyzed enantioselective diboration of various hydrocarbon starting materials to form stereodefined carbon-boron bonds is reported. The asymmetric Pt-catalyzed 1,4-diboration of <italic>trans</italic>-1,3-dienes provided 1,4-bis(boronate)esters in up to 98:2 er, representing the first enantioselective diene diboration. The enantioselective 1,2-diboration of <italic>cis</italic>-1,3-dienes and 4,4-disubstituted dienes afforded 1,2-bis(boronate)esters in up to 98:2 er. The intermediate allylboronates were utilized in aldehyde allylations to furnish polypropionate-like compounds and stereodefined carbon quaternary centers. The development of a Pt-catalyzed enantioselective diboration of terminal olefins is disclosed, giving the corresponding 1,2-diols in up to 97:3 er. Further optimization and expansion of the scope of this method is also discussed. / Thesis (PhD) — Boston College, 2011. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

The timing of glacial-interglacial cycles shows a clear dependence on the periodic variations in the Earth’s orbital parameters. However, the Earth’s climate is an extremely complex, non-linear system, with many internal feedback mechanisms and there are still features of the climate record for which a definitive explanation remains elusive. Understanding reef history is important due to significant predicted feedbacks between changes in global climate and carbonate production via the carbon cycle; phases of rapid reef growth in shallow water areas being associated with increased release of carbon dioxide to the atmosphere. Previous work on Pleistocene reef history, investigated via reef boreholes, shows a large global expansion of reefs between 800-400ka; approximately concurrent with one of the major unexplained alterations in the climate system, the Mid-Pleistocene Transition (MPT). Quaternary reef history is usually investigated via reef boreholes, which provide limited spatial information and are subject to dating uncertainties of the order of ±100kyrs. This means that any inferences made about the relationship between reef expansion and specific changes in the climate system are not well constrained. This thesis instead, presents a novel approach to reconstructing reef growth history, using a trial site near the island of New Caledonia, in the south west Pacific. The initiation of carbonate production on shallow shelves is known to produce a signal in the surrounding deeper basins, via sediment shedding. Therefore, this research set out to independently verify the proposed expansion of the New Caledonia Barrier Reef at ~ 400ka (Marine Isotope Stage [MIS] 11) by examining the composition of turbidites deposited in the New Caledonia Trough. Deep sea sediment core MD06-3019, was collected south west of the New Caledonia Barrier Reef (22oS, 165oE; 3,500m water depth). It is predominantly composed of pelagic carbonate ooze, into which 79 sandy turbidite layers have been deposited. These layers interrupt, but do not disturb, the background sedimentation and source material from the shallow shelf, which is carried to the deep sea via submarine canyons. A core age model based principally on orbital tuning, yields a core bottom age of 1,260ka, ~MIS38. This chronology has allowed the timing of deposition of the turbidite layers within the core to be assigned to within ±10kyr. Turbidite layers vary in width (1-35cm), grain size (φ=4 to -2) and composition, containing among other shelf derived material, well preserved coral fragments from 1.26Ma through to the present day. Patterns in turbidite timing and frequency, grain size and composition (investigated via point counting, carbonate coulometry and aragonite content) have been analysed, to assess whether there are any temporal changes which may reflect variation in shallow shelf reef extent. This included the development of XRF scanning measurements for [Sr], as a new proxy for the aragonite content of samples. A calibration line with the equation: Aragonite %=0.0011* Sr count +2.64 (R2 =0.6105, p-value < 0.001) was obtained for turbidite samples from sediment core MD06-3019. The method shows significant promise as a new proxy for quickly establishing the aragonite content of sediment samples. Corroborating the work of previous investigators, turbidites deposited since MIS11 show an increase in average bulk carbonate and aragonite content, a greater dominance of shallow water bioclasts and a higher occurrence of coral fragments. Additionally, both coarse and fine grained turbidites are present, whereas directly before this period only fine grained turbidites occur. However, there is another significant shift in depositional style further back in the record. Prior to MIS23 both coarse and fine grained turbidites are present, the average carbonate content of turbidite layers is higher and there is a greater dominance of shallow water biota. Coral abundance for turbidites at the base of the core can equal values for turbidites at the top of the core. These results challenge the assumption that the only significant evolution on the western New Caledonia margin over the last 1.2Myrs was the expansion of the barrier reef at MIS11. This suggests that the history of the western New Caledonia margin may be more complicated than initially anticipated. These temporal variations in turbidite deposition are interpreted as reflecting changes in the level of carbonate production on the shallow shelf over the course of the 1.26Myr record. Shallow water carbonate production having decreased substantially during the period MIS23-MIS11. There are many possible controls on the shallow water carbonate production; such as: sea surface temperature and salinity, sea-level and nutrient availability. However, it is hypothesised that the principal control is glacial-interglacial sea-level change. It is proposed that prior to MIS23 sea-level was high enough during certain interglacial periods for significant carbonate production to occur on the shelf. However, from MIS23 onwards the climate proceeded into a period of ‘lukewarm’ interglacials which were both cooler and had lower sea-levels. It is hypothesised that during this period sea-level did not rise enough during highstands to flood the shelf sufficiently to allow for significant shallow water carbonate production. The high sea-levels of the long, warm MIS11then allowed for the expansion of the barrier reef (perhaps on substrates provided by former siliciclastic coast lines, deposited between MIS23-11) and its continuation during subsequent interglacial periods until the current day. This pattern of shallow shelf carbonate production is similar to those proposed for the Belize margin and the Gulf of Papua over the last 1.2Myrs. This thesis provides one of the first detailed investigations of gravity deposits in the New Caledonia Trough, providing information on their composition and timing over an unprecedented 1.26Myr time period. This study demonstrates that deep sea turbidites, sourced from shallow shelf areas, can be used to help reconstruct tropical reef growth histories. The results corroborate the work of previous researchers in the area and provide new insights into the history of reefs along the western New Caledonian margin. The main advantage of this method, compared to traditional borehole techniques, is the 10-fold reduction in the age uncertainty of events, to ±10 kyr. In addition, because turbidite material is sourced from a wide area along the coast, the method is able to provide information on reef history over a larger spatial area than single reef boreholes. This method can now be extended globally to help improve knowledge of the timing and history of tropical reef growth during the Quaternary. This will enable a better understanding of how reefs have impacted on, and been affected by, changes in climate, linked by feedbacks mechanisms via the global carbon cycle.

No description available.

A dinâmica paleoceanográfica no Oceano Atlântico Sudoeste ainda é pouco conhecida, com a maioria dos trabalhos descrevendo os últimos 25 mil anos. Neste estudo, foram utilizados como indicadores as assembleias fósseis de cocolitoforídeos (também chamados de nanofósseis calcários), isótopos estáveis de oxigênio e carbono (em testas do foraminífero planctônico Globigerinoides ruber), o conteúdo de carbonato nos sedimentos (fração < 0,63 μm) e datações radiocarbônicas. Foram analisados dois testemunhos, coletados no talude da Bacia de Campos, compreendendo os últimos 440 mil anos. Os resultados apontam que espécies do grupo “placolitoformes”, como Gephyrocapsa spp. e Emiliania huxleyi, e a espécie Florisphaera profunda, habitante da zona fótica inferior, dominaram a assembleia durante todo o intervalo estudado. Entre 440 - 410 mil anos a produtividade é alta, independente da alternância entre estágios glaciais/interglaciais (EIMs 12, 11, 10, 9, 8, 7 e 6). Boa parte deste intervalo de tempo está relacionada ao evento Brunhes médio, quando, no hemisfério sul, havia uma intensificação das circulações atmosférica e oceânica, aumentando a ressurgência costeira. Nos últimos 130 mil anos, existe alguma relação entre a produtividade e esta ciclicidade climática. De forma geral, pode-se dizer que os estágios interglaciais stricto sensu (EIMs 5e e 1) são menos produtivos que os demais (EIMs 5d-a, 4, 3 e 2). Durante estágios interglaciais, a Zona de Convergência Intertropical estaria deslocada para o norte, os ventos de nordeste associados à Alta Subtropical do Atlântico Sul teriam baixa intensidade e a Corrente do Brasil estaria enfraquecida, levando à manutenção da estratificação das águas. Já durante o estágio glacial, as condições inversas favoreceriam a ressurgência costeira. Ao longo dos últimos 130 mil anos, a produtividade máxima é atingida entre 14 - 6,5 mil anos (durante a deglaciação), podendo ser um reflexo dos acontecimentos do Último Máximo Glacial. Entre 440 - 140 mil anos, cocolitoforídeos parecem ter um pequeno papel no ciclo do carbono, transferindo carbonato das águas superficiais para o fundo marinho. Este papel aumenta nos 130 mil anos subsequentes. Durante todo o intervalo, espécies produtoras de pequenos cocólitos, como Gephyrocapsa spp. e Emiliania huxleyi, são as mais determinantes nesta transferência, por serem muito abundantes. / The paleoceanographic dynamic of the Southweast Atlantic is still poorly known, with most of the studies describing the last 25×103 years. In this work, fossil assemblages of coccolithophorids (also called calcareous nannofossils), oxygen and carbon stable isotopes (in shells of the planktonic foraminifera Globigerinoides ruber), the carbonate content in the sediments (< 0,63 μm fraction) and radiocarbon dating were used as indicators. Two sediment cores, recovered at the slope of Campos Basin, were analyzed, comprising the last 440×103 years. The results show that placolith-bearing species, such as Gephyrocapsa spp. and Emiliania huxleyi, and the Florisphaera profunda species, which inhabits the lower photic zone, dominated the assemblage during the whole study interval. Between 440-410×103 years there is high productivity, independent of the alternation between glacial and interglacial stages (MISs 12, 11, 10, 9, 8, 7 and 6). Much of this time interval is related to the mid-Brunhes event, when an intensified atmospheric and oceanic circulation is reported in the southern hemisphere, leading to increased coastal upwelling. Over the past 130×103 years, there was some relationship between the productivity and this climate cyclicity. In a general way, it can be said that stricto sensu interglacial stages (MISs 5e and 1) are less productive than the others (MISs 5d-a, 4, 3 and 2). During interglacial stages, a northward shift in the Intertropical Convergence Zone position would take place, together with a weakening of the northeast winds associated to the Southern Atlantic Subtropical High and a weakening of the Brazil Current, leading to the maintenance of the water stratification. On the other hand, during the glacial stage, the inverse conditions would be favorable to coastal upwelling. Over the last 130×103 years, maximum productivity is achieved between 14- 6,5×103 years (during deglaciation), which could be a reflection of the events of the Last Glacial Maximum. Between 440-140×103 years, coccolithophorids seem to have had a small role in the carbon cycle, transferring carbonate shallow waters to the seabed. This role seems to have increased in the following 130×103 years. During the whole interval, species that produce small coccoliths, such as Gephyrocapsa spp. and Emiliania huxleyi, are the most crucial in this transfer, because they are very abundant.