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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.