Climate Forcing on Water Column and Sedimentary

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Climate Forcing on Water Column and Sedimentary DISSERTATION ZUR ERLANGUNG DES DOKTORGRADES DER NATURWISSENSCHAFTEN CLIMATE FORCING ON WATER COLUMN AND SEDIMENTARY ENVIRONMENTS OF AN ANCIENT SEMI-ENCLOSED BASIN: INSIGHTS FROM THE LATE MIOCENE (MESSINIAN) MEDITERRANEAN BASIN VON MATHIA SABINO HAMBURG, 2021 Photo by M. Sabino © M. Sabino Photo by GUTACHTER: PROF. DR. JÖRN PECKMANN PROF. DR. FRANCESCO DELA PIERRE FAKULTÄT FÜR MATHEMATIK, INFORMATIK UND NATURWISSENSCHAFTEN FACHBEREICH ERDSYSTEMWISSENSCHAFTEN, UNIVERSITÄT HAMBURG DISSERTATION ZUR ERLANGUNG DES DOKTORGRADES DER NATURWISSENSCHAFTEN CLIMATE FORCING ON WATER COLUMN AND SEDIMENTARY ENVIRONMENTS OF AN ANCIENT SEMI-ENCLOSED BASIN: INSIGHTS FROM THE LATE MIOCENE (MESSINIAN) MEDITERRANEAN BASIN VORGELEGT VON MATHIA SABINO AUS TURIN, ITALIEN AN DER FAKULTÄT FÜR MATHEMATIK, INFORMATIK UND NATURWISSENSCHAFTEN FACHBEREICH ERDSYSTEMWISSENSCHAFTEN DER UNIVERSITÄT HAMBURG HAMBURG, 2021 Als Dissertation angenommen am Fachbereich Erdsystemwissenschaften Tag des Vollzugs der Promotion: 26.04.2021 Gutachter: Prof. Dr. Jörn Peckmann Prof. Dr. Francesco Dela Pierre Vorsitzender des Fachpromotionsausschusses Erdsystemwissenschaften: Prof. Dr. Dirk Gajewski Dekan der Fakultät MIN: Prof. Dr. Heinrich Graener TABLE OF CONTENTS LIST OF PUBLICATIONS VII LIST OF ABBREVIATIONS IX ABSTRACT 1 KURZFASSUNG 3 CHAPTER 1 INTRODUCTION 6 1.1. THE MEDITERRANEAN BASIN IN THE LATE MIOCENE 6 1.2. THE MESSINIAN SALINITY CRISIS: STATE OF THE ART AND OPEN PROBLEMS 9 1.3. LIPID BIOMARKERS: A TOOL FOR UNRAVELING THE GEOLOGICAL PAST 12 1.4. THESIS OVERVIEW, RESEARCH QUESTIONS, AND SYNTHESIS OF THE KEY FINDINGS 15 CHAPTER 2 CLIMATIC AND HYDROLOGIC VARIABILITY IN THE NORTHERN MEDITERRANEAN ACROSS THE ONSET OF THE MESSINIAN SALINITY CRISIS 18 2.1. ABSTRACT 18 2.2. INTRODUCTION 19 2.3. GEOLOGICAL AND STRATIGRAPHIC SETTING 20 2.4. MATERIALS AND METHODS 23 2.5. RESULTS 26 2.6. DISCUSSION 29 2.7. CONCLUSIONS 35 2.8. ACKNOWLEDGMENTS 35 CHAPTER 3 THE RESPONSE OF WATER COLUMN AND SEDIMENTARY ENVIRONMENTS TO THE ADVENT OF THE MESSINIAN SALINITY CRISIS: INSIGHTS FROM AN ONSHORE DEEP-WATER SECTION (GOVONE, NW ITALY) 37 3.1. ABSTRACT 37 3.2. INTRODUCTION 37 3.3. GEOLOGICAL SETTING 39 3.4. MATERIALS AND METHODS 43 3.5. RESULTS 46 3.6. DISCUSSION 53 3.7. CONCLUSIONS 59 3.8. ACKNOWLEDGMENTS 59 CHAPTER 4 MARINE THAUMARCHAEOTA RECORD CARBON ISOTOPE EXCURSIONS IN THE NORTHERNMOST OFFSHOOT OF THE LATE MIOCENE MEDITERRANEAN BASIN 61 4.1. ABSTRACT 61 4.2. INTRODUCTION 61 4.3. MATERIALS AND METHODS 63 4.4. RESULTS AND DISCUSSION 65 4.5. SUMMARY AND IMPLICATIONS 68 4.6. ACKNOWLEDGMENTS 68 CHAPTER 5 SYNTHESIS AND FUTURE PERSPECTIVES 70 REFERENCE LIST 74 APPENDIX A 93 APPENDIX B 96 APPENDIX C 101 APPENDIX D 106 ACKNOWLEDGMENTS 120 VERSICHERUNG AN EIDES STATT – AFFIRMATION ON OATH 122 LIST OF PUBLICATIONS The thesis consists of two original articles (Chapter 2 and 3), both published in international, peer reviewed journals, and a third article (Chapter 4) currently under peer-review. For each of the articles my contribution was fundamental and is explained in detail in Appendix A. The original articles were slightly modified in their style to provide a consistent structure throughout the thesis. Figures were numbered continuously and references to Appendices are included. Sabino, M., Schefuß, E., Natalicchio, M., Dela Pierre, F., Birgel, D., Bortels, D., Schnetger, B., Peckmann, J., 2020. Climatic and hydrologic variability in the northern Mediterranean across the onset of the Messinian salinity crisis. Palaeogeography, Palaeoclimatology, Palaeoecology 545, article 109632. (Chapter 2) Sabino, M., Dela Pierre, F., Natalicchio, M., Birgel, D., Gier, S., Peckmann, J., 2020. The response of water column and sedimentary environments to the advent of the Messinian salinity crisis: insights from an onshore deep-water section (Govone, NW Italy). Geological Magazine, 1 – 17. (Chapter 3) Sabino, M., Birgel, D., Natalicchio, M., Dela Pierre, F., Peckmann, J. (submitted). Marine Thaumarchaeota record carbon isotope excursions in the northernmost offshoot of the late Miocene Mediterranean Basin. (Chapter 4) Data related to the already published articles were re-adapted from the author of the thesis for publication to the open access library PANGAEA (see Appendix A for details on contributions). Sabino, M., Schefuß, E., Natalicchio, M., Dela Pierre, F., Birgel, D., Bortels, D., Schnetger, B., Peckmann, J., 2020. Climate variability in the northern Mediterranean across the onset of the Messinian salinity crisis: insights from inorganic and organic geochemical proxies. PANGAEA. Sabino, M., Dela Pierre, F., Natalicchio, M., Birgel, D., Gier, S., Peckmann, J., 2021. Changes in water column and sedimentary environments at the onset of the Messinian salinity crisis: insights from an onshore deep-water section (Govone, NW Italy). PANGAEA. Additionally, I contributed to a fourth publication during my doctoral studies (see Appendix A for further details), which however has not been included in this work. Natalicchio, M., Dela Pierre, F., Birgel, D., Brumsack, H., Carnevale, G., Gennari, R., Gier, S., Lozar, F., Pellegrino, L., Sabino, M., Schnetger, B., Peckmann, J., 2019. Paleoenvironmental change in a precession-paced succession across the onset of the Messinian salinity crisis: insight from element geochemistry and molecular fossils. Palaeogeography, Palaeoclimatology, Palaeoecology 518, 45–61. (not included) VII LIST OF ABBREVIATIONS Al: aluminum OC: organic carbon APCI: atmospheric pressure P: precipitation chemical ionization PB: Piedmont Basin Ar.: Arnulfi Pentac. Bioz.: biozones sulfide: pentacyclic sulfide BIT: branched and isoprenoid Ph: phytane tetraether index PLG: Primary Lower Gypsum Bp-0: acyclic biphytane Poll. or Bp-1: monocyclic biphytane Pz.: Pollenzo Bp-2: bicyclic biphytane R: riverine runoff Bp-3: tricyclic biphytane SEM: scanning electron microscopy BSTFA: N,O-bis(trimethylsilyl)- Si: silicon trifluoracetamide SIM: single ion mode Cald.: caldarchaeol SPM: suspended particulate matter CPI: Carbon Preference Index SQ: scientific questions Cren.: crenarchaeol TC: total carbon DAGE: dialkyl glycerol ethers THM: tetrahymanol DCM: dichloromethane Ti: titanium DGD: diphytanyl glycerol diether TIC: total inorganic carbon DIC: dissolved inorganic carbon TLE: total lipid extract E: evaporation TOC: total organic carbon EDS: energy dispersive system TOM: terrestrial organic matter FAO: first abundant occurrence V-PDB: Vienna Pee Dee Belemnite FID: flame-ionization detector V-SMOW: Vienna Standard Mean G, Gov., Ocean Water Gv.: Govone XRD: X-ray diffraction GC: gas chromatograph XRF: X-ray fluorescence GDGT: glycerol dibiphytanyl Zr: zirconium glycerol tetraether HPLC: high performance liquid Symbols: chromatography 13C: carbon stable isotope ratio 13 IRMS: isotope ratio mass CBp: biphytane carbon stable spectrometer isotope ratio 13 IS: internal standard CDIC: dissolved inorganic carbon Isorenier.: isorenieratane stable isotope ratio kyr: thousand years 13 Cn-alk: n-alkane carbon stable Ly: lycopane isotope ratio Ma: million years 18O: oxygen stable isotope ratio Med.: Mediterranean 2H: hydrogen stable isotope ratio MeOH: methanol 2H : n-alkane hydrogen stable MGI, II, n-alk isotope ratio III: marine group I, II, III : biosynthetic fractionation MS: mass spectrometer MSC: Messinian salinity crisis factor n-alk.: n-alkane : sum IX ABSTRACT The late Miocene (11.6 to 5.3 Ma) was characterized by a global trend of cooling and aridification. In such a scenario, the Mediterranean Basin was experiencing increasing tectonic restriction and climate fluctuations driven by changes in orbital parameters of the Earth (mostly precession). The concurrence of these factors ultimately led to the most dramatic paleoceanographic event in the history of the basin, the Messinian salinity crisis (MSC; 5.97–5.33 Ma). Although this event is known since more than 50 years, a detailed understanding of the environmental conditions established at the onset and during the MSC has not been reached yet. This is due to the inaccessibility of sediments deposited in the Messinian Mediterranean depocenters (> 1000 m paleodepth), the lack of modern analogs, and the scarcity of body fossils in the stratigraphic record. A so far rarely explored possibility to solve the riddle of the enigmatic environmental change accompanying the MSC onset is the study of sediments deposited at intermediate paleobathymetric depths (200–1000 m). In fact, these sediments represent the link to the still inaccessible early MSC sediments deposited in the depocenters of the late Miocene Mediterranean. The aim of this thesis is to widen our knowledge on the paleoenvironmental conditions established at the MSC onset. Shale/marl couplets from intermediate paleobathymetric settings of the northernmost late Miocene Mediterranean sub- basin, the Piedmont Basin (NW Italy), were investigated. A multiproxy approach was applied, merging organic geochemical proxies (lipid biomarkers; compound- specific hydrogen (2H) and carbon (13C) stable isotopes) with inorganic geochemical proxies (Al, Si, Ti, and Zr; bulk-rock carbon (13C) and oxygen (18O) stable isotopes). Stratigraphic and petrographic studies complemented the investigations. One of the outcomes of this thesis is that prior to the onset of the MSC moister conditions prevailed at precession minima, resulting in enhanced riverine runoff. Such conditions favored phytoplankton blooms in the upper water column and led to a strong thermohaline stratification. Oxygen-depleted and sulfidic conditions developed
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