The climatic and environmental conditions during deposition of phosphorites and oil shales in the Late Cretaceous upwelling system of the Negev/Israel Dissertation zur Erlangung des Doktorgrades der Naturwissenschaften vorgelegt beim Fachbereich Geowissenschaften der Johann Wolfgang Goethe-Universität in Frankfurt am Main von Heiko Alsenz aus Bingen Frankfurt (2014) (D 30) Vom Fachbereich Geowissenschaften / Geographie der Johann Wolfgang Goethe-Universität als Dissertation angenommen. Dekan: Prof. Dr. Andreas Junge Gutachter: Prof. Dr. Wilhelm Püttmann Prof. Dr. Wolfgang Oschmann Prof. Dr. Silke Voigt Prof. Dr. Ruprecht Schleyer Datum der Disputation: 12. März 2015 Table of Contents Table of Contents List of Tables .............................................................................................................. 6 List of Figures ............................................................................................................. 7 Danksagung .............................................................................................................. 10 Abbreviations ........................................................................................................... 12 Zusammenfassung .................................................................................................... 13 Summary ................................................................................................................... 25 Introduction .............................................................................................................. 28 1 Sea surface temperature record of a Late Cretaceous tropical southern Tethys upwelling system ................................................................... 40 1.1 Abstract ...................................................................................................... 40 1.2 Introduction ................................................................................................ 40 1.3 Materials and methods ............................................................................... 43 1.3.1 Paleogeographical setting .............................................................. 43 1.3.2 Material and study sites ................................................................. 44 1.4 Sample preparation .................................................................................... 46 1.5 TEX86 analysis ........................................................................................... 47 1.6 Results ........................................................................................................ 50 1.7 Discussion .................................................................................................. 52 1.7.1 Late Cretaceous SSTs and cooling history .................................... 52 1.7.2 Late Cretaceous equatorial to polar SST gradient ......................... 57 1.7.3 Comparison of SSTs in inner and outer belts of the southern Tethyan upwelling system ............................................................. 58 1.8 Conclusion ................................................................................................. 60 2 Geochemical evidence for the link between sulfate reduction, sulfide oxidation and phosphate accumulation in a Late Cretaceous upwelling system ............................................................................................... 61 2.1 Abstract ...................................................................................................... 61 2.2 Introduction ................................................................................................ 62 2.3 Material and methods ................................................................................. 64 2.3.1 Location and samples .................................................................... 64 2.3.2 Sample preparation and analysis ................................................... 66 3 Table of Contents 2.4 Results and discussion ................................................................................ 68 2.4.1 TOC, TFe, TS and TP .................................................................... 68 2.4.2 Correlation of TOC and TS............................................................ 70 2.4.3 Correlation of TOC, TS and TFe ................................................... 72 2.4.4 Correlation of phosphate precipitation with sulfate reduction ....... 75 2.4.5 Fatty acid analysis .......................................................................... 79 2.5 Summary and conclusions .......................................................................... 82 3 Geochemical characterization of the Campanian/Maastrichtian upwelling system from Negev (Israel) and influence of natural sulfurization on the preservation of organic matter ...................................... 84 3.1 Abstract ...................................................................................................... 84 3.2 Introduction ................................................................................................ 84 3.3 Material and methods ................................................................................. 87 3.3.1 Location and samples ..................................................................... 87 3.3.2 Sample preparation and analysis .................................................... 88 3.4 Results and discussion ................................................................................ 88 3.4.1 Molecular composition of hydrocarbons ....................................... 89 3.4.1.1 Straight chain alkanes ....................................................... 89 3.4.1.2 C27-C29 Steranes ................................................................ 91 3.4.1.3 Indicators of paleosalinity (chromans) ............................. 92 3.4.1.4 Pentacyclic triterpanes ...................................................... 94 3.4.1.5 Straight chain and C20-isoprenoid thiophenes .................. 95 3.4.1.6 C27‒C29-Epithiosteranes .................................................... 97 3.4.1.7 Sulfur containing hopanoids ............................................. 99 3.4.1.8 Degree of OM sulfurization ............................................ 104 3.5 Summary and conclusions ........................................................................ 106 4 Paleoceanographic reconstruction of the Late Cretaceous oil shale of the Negev, Israel: Integration of geochemical, and stable isotope records of the organic matter ......................................................................... 107 4.1 Abstract .................................................................................................... 107 4.2 Introduction .............................................................................................. 108 4 Table of Contents 4.2.1 The high-productivity sequence in Israel .................................... 108 4.2.2 Background on the foraminiferal assemblages ............................ 110 4.3 Materials and methods ............................................................................. 111 4.3.1 Location and samples .................................................................. 111 4.3.2 Sample analyses ........................................................................... 113 4.4 Results ...................................................................................................... 116 4.4.1 TOC, TON and C/N ..................................................................... 116 4.4.2 Pristane/Phytane (Pr/Ph) ratio ...................................................... 117 4.4.3 Organic N and C isotopes ............................................................ 117 4.4.4 Organic petrology ........................................................................ 117 4.5 Discussion ................................................................................................ 118 4.5.1 TOC ............................................................................................. 118 4.5.2 Organic petrology ........................................................................ 118 4.5.3 TON and C/N ratio ...................................................................... 119 4.5.4 Pr/Ph ratio .................................................................................... 121 13 4.5.5 δ Corg ........................................................................................... 122 15 4.5.6 δ Norg .......................................................................................... 125 4.5.7 The depositional environment of the Negev high productivity sequence: integration of geochemical and foraminiferal characteristics .............................................................................. 126 4.6 Summary .................................................................................................. 127 5 Conclusions and future implications ............................................................. 130 5.1 Paleoclimatic changes and paleo sea surface temperature of the upwelling system ..................................................................................... 130 5.2 Natural sulfurization ................................................................................ 131 5.3 Phosphate deposition in the context of sulfate reduction and sulfide oxidation .................................................................................................. 132 5.4 Bulk