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Selenium (Se) is an essential trace element, which, with multiple oxidation states and six stable isotopes, has the potential to be a powerful paleo-environmental proxy. In this study, Se concentrations and isotopic compositions were analyzed in a suite of about 120 samples of fine-grained marine sedimentary rocks and sediments spanning the entire Phanerozoic. While the selenium concentrations vary greatly (0.22 to 72 ppm), the δ82/76Se values fall in a fairly narrow range from -1 to +1 , with the exception of laminated black shales from the New Albany Shale formation (Devonian), which have δ82/76Se values of up to +2.20 . Black Sea sediments (Holocene) and sedimentary rocks from the Alum Shale formation (Late Cambrian) have Se/TOC ratios and δ82/76Se values close to those found in modern marine plankton (1.72x10-6±1.55x10-7 mol/mol and 0.42±0.22 ). (Note: TOC = total organic carbon.) For the other sedimentary sequences, the Se/TOC ratios indicate enrichment in selenium relative to marine plankton. Additional input of isotopically light terrigenous Se (δ82/76Se ≈ -0.42 ) may explain the Se data measured in recent Arabian Sea sediments (Pleistocene). The very high Se concentrations in sedimentary sequences that include the Cenomanian-Turonian Ocean Anoxic Event (OAE) 2 possibly reflect a significantly enhanced input of volcanogenic Se to the oceans. As the latter has an isotopic composition (δ82/76Se ≈ 0 ) not greatly different from marine plankton, the volcanogenic source does not impart a distinct signature to the sedimentary Se isotope record. The lowest δ82/76Se values are observed in the OAE2 samples from Demerara Rise and Cape Verde Basin cores (δ82/76Se = -0.95 to 1.16 ) and are likely due to fractionation associated with microbial or chemical reduction of Se oxyanions in the euxinic water column. In contrast, a limiting availability of seawater Se during periods of increased organic matter burial is thought to be responsible for the elevated δ82/76Se values and low Se/TOC ratios in the black shales of the New Albany Shale formation. Overall, our results suggest that Se data may provide useful information on paleodepositional conditions, when included in a multi-proxy approach.

In this thesis I document the biostratigraphy of two Cretaceous sections in Pakistan, the Chichali Nala Section and the Moghal Kot Section. Furthermore, I document the stratigraphy of the so-called Oceanic Anoxic Events (OAEs) in the Moghal Kot Section. In addition, I establish potential links between the planktonic foraminiferal evolution and these OAEs in the Moghal Kot Section. Sea Surface Temperatures (SSTs) are established for the Valanginian time by using the TEX86 and δ18O proxies in the Chichali Nala Section. The new biostratigraphy of the Chichali Nala Section shows that the ages of the sediments are mainly Valanginian. The biostratigraphy of the Moghal Kot Section show ranges in age from the Early Aptian to Early Maastrichtian. Seven OAEs were recorded in the Moghal Kot Section based on the combined study of biostratigraphy, microfacies, and δ13C analysis. These OAEs correlate well with previously documented OAEs elsewhere, therefore the new record of the OAEs in the Moghal Kot Section confirms the widespread occurrence of these events, possibly all global in nature. A quantitative review of the planktonic foraminiferal evolution in the Moghal Kot Section indicates that the environmental changes along the OAE2 have strongly forced the evolution of the planktonic foraminifera. Conversely, no clear relationship is observed between other OAEs and planktonic foraminiferal evolution in the same section. The SST results based on the TEX86 in the Chichali Nala Section show that the surface ocean was consistently much warmer (10-12 oC) than today at the paleolatitude of ~-35o during the Valanginian time. Such warm conditions are also supported by the spore and pollen assemblages of the Chichali Nala Section. Collectively the two datasets indicate strongly that the Valanginian world was overall extremely warm. Such warming during the Valanginian is incompatible with previously suggested cooler conditions during this time period.

The applications of calcium-isotope measurements in marine carbonates are explored in several different contexts within this thesis. As a record of global ion fluxes, seawater calcium-isotope ratios can be used as tracers for large weathering imbalances, which develop as a feedback system in response to intervals of climate change. This approach provides valuable constraints on the complex climatic and oceanographic phenomena known as the Oceanic Anoxic Events. Over much longer timescales, the calcium-isotope ratio of seawater is influenced by steady-state processes that reflect the evolution of seawater chemistry. To understand these influences, the modern calcium-isotope budget is assessed quantitatively using a compilation of marine carbonate samples, revealing several distinctive components of the carbonate burial sink that can affect the steady-state balance of the calcium cycle. Changes in the major ion composition of seawater and in the organisms that contribute to sedimentary carbonate burial are shown to contribute significantly to the geological record of seawater calcium-isotope ratios. The importance of skeletal carbonate in the calcium cycle leads to another application of calcium isotopes towards understanding biomineralization. This large and complex topic is approached with calcium-isotope data from two unique growth experiments that constrain some of the mechanisms by which biogenic aragonite acquires its geochemical signatures. This range of topics presents a diverse, but by no means exclusive, sample of the topics that are accessible for investigation through calcium-isotope analysis. The potential of this isotopic tool is demonstrated by the breadth of environments and timescales represented in this work.

Fire is a natural process that has existed on our planet for more than ~350 million years, and is a process that continues to influence our everyday lives. On Earth, a relationship exists between the process of combustion and the natural functioning of the Earth system. Here, the process of combustion has been implicated in playing an essential role for life on Earth, where natural Earth system processes have been shown to influence ignition probability, fire spread and fire behaviour, and where fire can provide a variety of feedbacks, to the Earth system over different timescales. Over medium timescales of decades to hundreds of thousands of years, the likelihood and behaviour of fires are controlled by regional climate changes and vegetation type, whilst the occurrence of fire can play a crucial role in influencing biome persistence and development. Over long timescales (hundreds of thousands to multi-million year), the components influencing the probability of fire and fire behaviour not only involve processes occurring over local and regional spatial scales, and over short and medium timescales, but also long term processes occurring globally, such as changes in atmospheric oxygen concentration and the evolution of vegetation. Across these timescales in Earth’s past, combustion has been shown to impact global ecosystems, climate and the carbon cycle by generating feedbacks that influence Earth’s biogeochemical cycles. However, it is clear that our understanding of the role that fire plays in the Earth system, although improving is still developing. This thesis provides an analysis of these Earth system - fire relationships and feedbacks across medium and long timescales in deep time, in order to understand the role that fire may have played and what the record of fire can tell us about the functioning and re-equilibrating of the Earth system during and after significant carbon-cycle perturbation events occurring in Earth’s deep past. The results presented in this thesis contribute what is believed to be the first fossil evidence that rising atmospheric oxygen and fire feedbacks may have aided in the termination of a significant carbon-cycle perturbation event, termed the ‘Toarcian oceanic anoxic event’ that occurred ~183 million years ago during the Jurassic period, and the return of the Earth system towards ‘background functioning’. This thesis also provides an analysis of the record of wildfire in the form of fossil charcoal across the initiation of an anoxic event that occurred ~93 million years ago, during the Cretaceous period. The results illustrate that CO2 - climate driven changes in wildfire activity can be observed across medium timescales even during times of significant carbon-cycle perturbations, and modelled high atmospheric oxygen concentrations. These results illustrate how hypothesized changes in the hydrological cycle, and likely moisture content of fuel, appear to be the dominant control on wildfire activity during this period. Finally, this thesis provides an analysis of charcoal abundance variations occurring across natural, orbitally forced cycles, termed the Milankovitch cycles. The results presented illustrate that natural variations in charcoal abundance are possible over intermediate timescales within the geological record. This thesis therefore illustrates a need to take into consideration and incorporate ‘natural background’ fluctuations in fire activity occurring over medium timescales, when analysing and predicting past and future climate change patterns.

An important episode of carbon sequestration, Oceanic Anoxic Event 1a (OAE-1a), characterizes the Lower Aptian worldwide, and is mostly known from deeper-water settings. The present work of two Lower Aptian deposits, Madotz (N Spain) and Curití Quarry (Colombia), is a multiproxy study that includes fossil assemblages, microfacies, X-ray diffraction bulk and clay mineralogy, elemental analyses (major, minor, trace elements), Rock-Eval pyrolysis, biomarkers, inorganic and organic carbon content, and stable carbon isotopes. The results provide baseline evidence of the local and global controlling environmental factors influencing OAE-1a in shallow-water settings. The data also improve our general understanding of the conditions under which organic-carbon-rich deposits accumulate. The sequence at Madotz includes four intervals (Unit 1; Subunits 2a, 2b and 2c) that overlap the times prior to, during and after the occurrence of OAE-1a. The Lower Unit 1(3m thick) is essentially siliciclastic, and Subunit 2a (20m) contains Urgonian carbonate facies that document abruptly changing platform conditions prior to OAE-1a. Subunit 2b (24.4 m) is a mixed carbonate-siliciclastic facies with orbitolinid-rich levels that coincides with OAE-1a δ13C stages C4-C6, and is coeval with the upper part of the Deshayesites forbesi ammonite zone. Levels with pyrite and the highest TOC values (0.4-0.97%), interpreted as accumulating under suboxic conditions, and are restricted to δ13C stages C4 and C5. The best development of the suboxic facies is at the level representing the peak of the transgression. Subunit 2c, within δ13C stage C7, shows a return of the Urgonian facies. The 23.35-m section at Curití includes a 6.3-m interval at the base of the Paja Formation dominated by organic-rich marlstones and shales lacking benthic fossils and bioturbation, with TOC values as high as 8.84%. The interval overlies a level containing reworked and phosphatized assemblages of middle Barremian to lowest Aptian ammonites. The range of values and the overall pattern of the δ13Corg (-22.05‰ to -20.47‰) in the 6.3m-interval is comparable with Lower Aptian δ13C stage C7. Thus, conditions of oxygen depletion at this site also occurred after Oceanic Anoxic Event-1a, which developed between carbon isotope stages C3 and C6. Both sites, Madotz and Curití, attest to the importance of terrigenous and nutrient fluxes in increasing OM productivity that led to episodic oxygen deficiency.

O Cretáceo inferior é caracterizado por mudanças drásticas em todos os envelopes terrestres, envolvendo desde variações geodinâmicas a importantes mudanças paleoclimáticas. Entretanto, há poucos registros desses eventos no hemisfério sul, sendo o DSDP-511 o principal deles. Com objetivo de gerar melhores vínculos temporais para os registros do Cretáceo Inferior no hemisfério sul, foram realizados estudos paleomagnéticos e de magnetismo ambiental em alta resolução espacial em uma secção do sítio DSDP-511 (núcleos 58 e 59), a qual corresponde ao intervalo entre 508,77 a 523,94 mbsf (meters below sea floor) e abrange os estágios Barremiano e Aptiano. A compreensão dos eventos paleoclimáticos neste sítio não é trivial, uma vez que, além de ambiguidade nas idades inferidas pela bioestratigrafia, apenas parte do evento de anoxia oceânica OAE 1a está registrada devido a uma lacuna de amostragem. Foram identificados dois principais portadores magnéticos através da análise de curvas de aquisição e desmagnetização de magnetização remanente anisterética (ARM) e magnetização remanente isotérmica (IRM). O mineral de baixa corecividade é a magnetita, confirmada a partir da desmagnetização de IRM triaxial. Sua origem é provavelmente detrítica. O portador de alta coercividade foi interpretado como hematita. A contribuição relativa dos portadores magnéticos apresentou uma variação acentuada no intervalo entre 512 e 514 mbsf, sendo manifestada através de um pico em todos os parâmetros de magnetismo ambiental. Esta variação está associada também à maior concentração de minerais magnéticos neste intervalo e coincide com um marcado aumento na temperatura da superfície dos oceanos. Após desmagnetização progressiva e identificação da componente magnética característica foram definidas duas zonas de polaridade normal e uma zona de polaridade reversa (518,9 e 518,16 mbsf). Além disso, foi definida uma zona discreta de polaridade reversa em 509,20 mbsf. Os resultados encontrados apresentam diferenças significativas quando comparadas com estudos anteriores no mesmo testemunho. Uma datação Re-Os em folhelhos negros de 125,3 ± 2,2 Ma entre 519,01 e 519,40 mbsf foi obtida recentemente e forneceu um vínculo absoluto de idade para o intervalo estudado. O padrão de reversões encontrado foi compatível com a presença dos chrons M0r e ISEA. O modelo de idades proposto permite reposicionar o evento OAE 1a entre as profundidades 513,5 a 518 mbsf, incluindo a parte não recuperada do testemunho. Esta interpretação também compatível com dados de TOC e de 13C obtidos recentemente por outros autores. / The lower Cretaceous is characterized by drastic changes in the Earth, from geodynamic variations to important paleoclimatic changes. However, there are few records of these events in the southern hemisphere, the DSDP-511 being the most comprehensive one. In order to provide better temporal constraints for the lower Cretaceous records in the southern hemisphere, paleomagnetic and high-resolution environmental magnetism studies were performed in a section of the DSDP-511 site (cores 58 and 59), which corresponds to the interval between 508.77 to 523.94 mbsf (meters below sea floor) and covers the Barremian and Aptian stages. The correct assessment of paleoclimatic events at this site is not trivial because, in addition to the ambiguity at the ages inferred by biostratigraphy, only part of the OAE 1a (oceanic anoxic event) was recovered. Two main magnetic carriers were identified through the analysis of acquisition and demagnetization of anhysteretic remanent magnetization (ARM) and isothermal remanent magnetization (IRM) curves. The low coercivity mineral is magnetite, as attested by triaxial IRM demagnetization. Its origin is likely detrital. The high coercivity carrier was interpreted as hematite. The relative contribution of magnetic carriers has a strong variation in the interval between 512 and 514 mbsf, being manifested by a peak in all parameters of environmental magnetism. This variation is also associated with the higher concentration of magnetic minerals and coincides with a marked increase in the sea surface temperature in this interval. After stepwise demagnetization and identification of the characteristic magnetic component, two zones of normal polarity and a zone of reverse polarity (518.9 and 518.16 mbsf) were defined. In addition, a discrete zone of reverse polarity was defined at 509.20 mbsf. The results obtained present significant differences when compared with previous studies in the same core. A Re-Os dating on black shales of 125.3 ± 2.2 Ma between 519.01 and 519.40 mbsf was obtained recently and provided an absolute constraint onto which the polarity zones could be matched. The pattern of reversions found is compatible with the presence of chrons M0r and ISEA. The proposed age model allows repositioning the OAE 1a event between depths 513.5 to 518 mbsf in the core and overlap the unrecovered part. This interpretation is also compatible with TOC and 13C data recently obtained by other authors.

O Cretáceo inferior é caracterizado por mudanças drásticas em todos os envelopes terrestres, envolvendo desde variações geodinâmicas a importantes mudanças paleoclimáticas. Entretanto, há poucos registros desses eventos no hemisfério sul, sendo o DSDP-511 o principal deles. Com objetivo de gerar melhores vínculos temporais para os registros do Cretáceo Inferior no hemisfério sul, foram realizados estudos paleomagnéticos e de magnetismo ambiental em alta resolução espacial em uma secção do sítio DSDP-511 (núcleos 58 e 59), a qual corresponde ao intervalo entre 508,77 a 523,94 mbsf (meters below sea floor) e abrange os estágios Barremiano e Aptiano. A compreensão dos eventos paleoclimáticos neste sítio não é trivial, uma vez que, além de ambiguidade nas idades inferidas pela bioestratigrafia, apenas parte do evento de anoxia oceânica OAE 1a está registrada devido a uma lacuna de amostragem. Foram identificados dois principais portadores magnéticos através da análise de curvas de aquisição e desmagnetização de magnetização remanente anisterética (ARM) e magnetização remanente isotérmica (IRM). O mineral de baixa corecividade é a magnetita, confirmada a partir da desmagnetização de IRM triaxial. Sua origem é provavelmente detrítica. O portador de alta coercividade foi interpretado como hematita. A contribuição relativa dos portadores magnéticos apresentou uma variação acentuada no intervalo entre 512 e 514 mbsf, sendo manifestada através de um pico em todos os parâmetros de magnetismo ambiental. Esta variação está associada também à maior concentração de minerais magnéticos neste intervalo e coincide com um marcado aumento na temperatura da superfície dos oceanos. Após desmagnetização progressiva e identificação da componente magnética característica foram definidas duas zonas de polaridade normal e uma zona de polaridade reversa (518,9 e 518,16 mbsf). Além disso, foi definida uma zona discreta de polaridade reversa em 509,20 mbsf. Os resultados encontrados apresentam diferenças significativas quando comparadas com estudos anteriores no mesmo testemunho. Uma datação Re-Os em folhelhos negros de 125,3 ± 2,2 Ma entre 519,01 e 519,40 mbsf foi obtida recentemente e forneceu um vínculo absoluto de idade para o intervalo estudado. O padrão de reversões encontrado foi compatível com a presença dos chrons M0r e ISEA. O modelo de idades proposto permite reposicionar o evento OAE 1a entre as profundidades 513,5 a 518 mbsf, incluindo a parte não recuperada do testemunho. Esta interpretação também compatível com dados de TOC e de 13C obtidos recentemente por outros autores. / The lower Cretaceous is characterized by drastic changes in the Earth, from geodynamic variations to important paleoclimatic changes. However, there are few records of these events in the southern hemisphere, the DSDP-511 being the most comprehensive one. In order to provide better temporal constraints for the lower Cretaceous records in the southern hemisphere, paleomagnetic and high-resolution environmental magnetism studies were performed in a section of the DSDP-511 site (cores 58 and 59), which corresponds to the interval between 508.77 to 523.94 mbsf (meters below sea floor) and covers the Barremian and Aptian stages. The correct assessment of paleoclimatic events at this site is not trivial because, in addition to the ambiguity at the ages inferred by biostratigraphy, only part of the OAE 1a (oceanic anoxic event) was recovered. Two main magnetic carriers were identified through the analysis of acquisition and demagnetization of anhysteretic remanent magnetization (ARM) and isothermal remanent magnetization (IRM) curves. The low coercivity mineral is magnetite, as attested by triaxial IRM demagnetization. Its origin is likely detrital. The high coercivity carrier was interpreted as hematite. The relative contribution of magnetic carriers has a strong variation in the interval between 512 and 514 mbsf, being manifested by a peak in all parameters of environmental magnetism. This variation is also associated with the higher concentration of magnetic minerals and coincides with a marked increase in the sea surface temperature in this interval. After stepwise demagnetization and identification of the characteristic magnetic component, two zones of normal polarity and a zone of reverse polarity (518.9 and 518.16 mbsf) were defined. In addition, a discrete zone of reverse polarity was defined at 509.20 mbsf. The results obtained present significant differences when compared with previous studies in the same core. A Re-Os dating on black shales of 125.3 ± 2.2 Ma between 519.01 and 519.40 mbsf was obtained recently and provided an absolute constraint onto which the polarity zones could be matched. The pattern of reversions found is compatible with the presence of chrons M0r and ISEA. The proposed age model allows repositioning the OAE 1a event between depths 513.5 to 518 mbsf in the core and overlap the unrecovered part. This interpretation is also compatible with TOC and 13C data recently obtained by other authors.

Rare earth elements (REEs) and their isotopes (such as Nd isotopes) can be potentially used to trace a wide range of oceanic processes in both modern and ancient oceans, but their successful application as tracers requires a comprehensive understanding of REE cycling in the modern ocean. Previous studies of REEs in seawater were largely constrained by analytical difficulties in generating accurate and precise REE data from seawater, which typically contain REE concentrations at a sub-ppt to ppt level. A new, and relatively simple, analytical method for precise and accurate determination of all dissolved REE concentrations in reasonably small (∼100 ml) seawater samples is presented in this thesis. With the application of the new method, this thesis reports the first full-depth, zonal ocean section of all dissolved REE concentrations, collected during the CoFeMUG cruise along ∼12°S in the South Atlantic. The section approach of this study places the distribution of dissolved REE concentrations in a well-constrained hydrographic context, allowing the first quantitative assessment (by an inverse model) of the relative importance of hydrographic controls resulting from advection/mixing of ocean circulation, together with non-conservative controls resulting from local particle scavenging and remineralization, in controlling the distribution of dissolved REEs in this region. A noteworthy decoupling of Ce and Mn with respect to their cycling in the water column was also observed in this study. The application of Nd isotopes as a tracer to reconstruct changes in ocean circulation in the NW European chalk shelf sea during rapid climatic events, including the mid-Cenomanian Event and oceanic anoxic event 2 (OAE 2), suggests a tight coupling between ocean circulation and transient climatic cooling during the general warm Late Cretaceous. An advected volcanic signal during OAE 2 was registered in the seawater Nd-isotope record from the English Chalk, probably suggesting a period of enhanced ocean ventilation/mixing at this time.