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Fire & Global Change During Key Intervals of the Late Triassic & Early Jurassic with a Focus on the Central Polish Basin

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Fire & Global Change During Key Intervals of the Late Triassic & Early Jurassic with a Focus on the Central Polish Basin FIRE & GLOBAL CHANGE DURING KEY INTERVALS OF THE LATE TRIASSIC & EARLY JURASSIC WITH A FOCUS ON THE CENTRAL POLISH BASIN Submitted by Robyn Pointer to the University of Exeter as a thesis for the degree of Doctor of Philosophy in Geology, in November 2018. This thesis is available for Library use on the understanding that it is copyright material and that no quotation from the thesis may be published without proper acknowledgement. I certify that all material in this thesis which is not my own work has been identified and that no material has been previously submitted and approved for the award of a degree by this or any other University. Signature……………………………………………… 2 ABSTRACT Core from modern-day Poland recovering fluvial and paralic strata provides an excellent record of climatic and environmental changes in the Central Polish Basin during two key intervals of the Early Jurassic. Thick successions of Rhaetian-Hettangian and Pliensbachian-Toarcian age are examined using a number of techniques in order to understand the wildfire activity history, carbon- cycle interactions, and organic matter composition of sediments at two sites in the Central Polish Basin. Physical and geochemical proxies for wildfire activity show evidence of increased wildfire activity both prior to and after the Toarcian Oceanic Anoxic Event (OAE) at the Kazewy-1 site, with suppression of wildfire activity during the negative carbon-isotope excursion of the OAE. Correlation with published wildfire activity proxy records from additional sites in the Tethyan realm shows that this pattern was not limited to the Central Polish Basin, but is part of a wider, regional change. Additionally, new wildfire activity proxy records show increased wildfire activity across the Triassic-Jurassic Boundary at the Kaszewy- 1 and Niekłań PIG-1 sites in the Central Polish Basin, correlating with other contemporaneous proxy records from Denmark and Greenland. New carbon- isotope records generated from terrestrial organic matter from the Niekłań PIG-1 core show trends towards heavier δ13C values immediately after the Triassic- Jurassic Boundary, providing evidence of a perturbation to the carbon-cycle at this time. Exploratory investigation of sediments from the Kaszewy-1 core provides a new record of BIT indices of Early Jurassic sediments, surpassing the oldest-known use of this terrestrial organic matter input proxy. Additionally, a newly-developed technique is used to investigate carbon-isotope variability in fossil terrestrial organic matter across the Toarcian Oceanic Anoxic Event carbon-isotope excursions. A new record of individual phytoclast δ13C values demonstrates that, despite δ13C variability between phytoclasts from a single horizon, larger overall trends in δ13C values can be identified from single phytoclast δ13C measurements. 3 4 ACKNOWLEDGEMENTS The work presented in this thesis would not have been possible without the assistance of the following people, and I would like to acknowledge and thank them for their help: Prof. Stephen P. Hesselbo, Camborne School of Mines, University of Exeter, for continuous, invaluable supervision, guidance, and support over the last 4 years. Without his assistance, this thesis simply would not be. Dr. Claire Belcher, wildFIRE Lab, University of Exeter, for continuous supervision, guidance, and support over the last 4 years. Dr. Kate Littler, Camborne School of Mines, University of Exeter, for continuous supervision, guidance, and support over the last 4 years, and for sample collection in the field. Prof. Grzegorz Pieńkowski, Polish Geological Institute – National Research Institute, for facilitating access to sample material held by the Polish Geological Institute, for guidance and assistance with sample collection in the field, and for general guidance on the topic of the Early Jurassic in the Polish Basin. Dr. Sarah Baker, wildFIRE Lab, University of Exeter, for guidance and assistance with processing of sample material for fossil charcoal analyses, and for providing sample material for the single phytoclast carbon-isotope values study. Sam Barker, formerly of the Environment and Sustainability Institute, University of Exeter, for guidance and assistance with carbon-isotope analyses of sample material from the Polish Basin. Dr. Sargent Bray and Dr. Jessica Whiteside, Organic Geochemistry and Compound Specific Isotope Ratio Mass Spectrometry Laboratory, University of Southampton, for facilitating collaborative polycyclic aromatic hydrocarbon analyses, and for guidance and assistance with laboratory work and data interpretation. Dr. Mark Grosvenor, wildFIRE Lab, University of Exeter, for guidance and assistance with processing of sample material for fossil charcoal analyses. 5 Dr. Marta Hodbod, Polish Geological Institute – National Research Institute, for providing sample material for carbon-isotope analyses. Prof. Melanie Leng, Stable Isotope Facility, British Geological Survey, for carbon-isotope analyses of sample material. Dr. Clemens V. Ullmann, Camborne School of Mines, University of Exeter, for assistance with sample collection in the field. Linda van Roij and Prof. Dr. Appy Sluijs, Department of Earth Sciences, Utrecht University, for facilitating collaborative single phytoclast carbon- isotope analyses, and for guidance and assistance with laboratory work and data interpretation. Dr. Christopher Vane and Dr. Raquel A. dos Santos, Organic Geochemistry Facility, British Geological Survey, for the processing and analysis of samples for the BIT index study. I would also like to thank my family and my partner for their unconditional support and encouragement over the last 4 years, as well as all of the new friends I’ve made during my time at Camborne School of Mines who helped to celebrate the good times, and to endure the hard times. 6 CONTENTS LIST OF FIGURES & TABLES IN THIS THESIS …………………………………………...16 ABBREVIATIONS USED IN THIS THESIS ………………………………………………...30 CHAPTER 1 INTRODUCTION ……………………………………………………...….31 CHAPTER 2 THESIS AIMS ……………………………………………………………35 CHAPTER 3 INDICATORS OF GLOBAL CHANGE AND VARIATIONS IN WILDFIRE ACTIVITY ………………………………………………………………………………………….36 3.1. Global Changes Across the Triassic-Jurassic Boundary …….…….……36 3.1.1. Defining the Triassic-Jurassic Boundary & Correlation Issues …....36 3.1.2. Environmental Conditions Across the T-J Boundary & Their Effects …………………………………………………………………………………...38 3.1.2.1. The End-Triassic Mass Extinction & Possible Causes ……..…39 3.1.3. Carbon-isotope Stratigraphy …………………………………….….…41 3.1.3.1. The Marine δ13Corg & δ13Ccarb Records ………………….……41 3.1.3.2. The Terrestrial δ13Corg Record ……………………………….….45 3.1.3.3. Possible Causes of the T-J Boundary Negative δ13C Excursions ………………………………………………………………………………..46 3.2. Global Changes During the Toarcian ………………………………………51 3.2.1. Environmental Conditions During the Toarcian ……………………..51 3.2.2. Organic and Inorganic Carbon-isotope Stratigraphy ……………….52 3.2.2.1. Causes of the Toarcian OAE Negative CIEs …………………..53 3.3. The Polish Basin: Early Jurassic Records ………………………………..54 3.3.1. Lower Jurassic Stratigraphy of the Polish Basin ……………………55 3.3.2. Environmental Conditions in the Polish Basin During the Early Jurassic ………………………………………………………………………...60 3.3.2.1. The Triassic-Jurassic Boundary ……………………………...…60 Contents 3.3.2.2. The Toarcian ……………………………………………….……..62 3.3.3. Previous Studies & Scope for Future Work ………………………....62 3.4. Carbon-isotopes in Organic Matter ………………………………………...64 3.4.1. A Brief Introduction to Stable Carbon-isotopes and δ13C Values ….64 3.4.2. Carbon-isotope Variability in Organic Matter ………………………..65 3.4.3. Carbon-isotope Signatures of Plants …………………………………66 3.4.3.1. Intrinsic Factors ……………………………………………………66 3.4.3.2. External Factors …………………………………………………..69 3.5. Wildfire Activity in the Fossil Record ………………………………………71 3.5.1. Physical Evidence: Fossil Charcoal ………………………………….71 3.5.1.1. Fossil Charcoal: Characteristics, Formation & Identification ...71 3.5.1.2. Fossil Charcoal as an Indicator of Past Wildfire Activity ……..72 3.5.2. Geochemical Evidence: Pyrolytic Polycyclic Aromatic Hydrocarbons …………………………………………………………………………………...76 3.5.2.1. Polycyclic Aromatic Hydrocarbons: Formation & Characteristics ………………………………………………………………………………..76 3.5.2.2. Pyrolytic PAHs as Indicators of Past Wildfire Activity ………...79 3.5.3. Causes of Changes in Wildfire Activity Levels ………………………80 3.5.3.1. Initiation of Wildfires ………………………………………………80 3.5.3.2. Factors Influencing Wildfire Activity Level ………………………82 3.5.4. Wildfire Activity During the Early Jurassic ……………………………87 3.5.4.1. The Triassic-Jurassic Boundary …………………………………87 3.5.4.2. The Toarcian Oceanic Anoxic Event ……………………………89 3.6. The BIT and MBT’-CBT indices …………………………………………….90 3.6.1. The BIT Index …………………………………………………………..90 8 Contents 3.6.2. The MBT’-CBT Index …………………………………………………..91 CHAPTER 4 LABORATORY METHODS USED IN THIS THESIS ………………………..93 4.1. Single-phytoclast δ13C Measurements …………………………………….93 4.1.1. St Audrie’s Bay, UK, Samples ………………………………………...93 4.1.2. Llanbedr, Wales, UK, Samples ………………………………………..97 4.2. Fossil Charcoal Quantification ……………………………………………..99 4.2.1. Acid Maceration & Sieving …………………………………………….99 4.2.2. Coarse Fraction Preparation & Particle Quantification …………….99 4.2.3. Fine Fraction Preparation & Particle Quantification ……………….101 4.3. Polycyclic Aromatic Hydrocarbon Quantification ………………………..102 4.3.1. Extraction & Separation of Polycyclic Aromatic Hydrocarbons from Sediments …………………………………………………………………….102 4.3.2. Analysis
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