Establishing Geochemical Constraints on Mass Accumulation Rates Across the Cretaceous-Paleogene Boundary With Extraterrestrial Helium-3 by Marie Minh-Thu Giron B.S. Geology California Institute of Technology, 2009 SUBMITTED TO THE DEPARTMENT OF EARTH, ATMOSPHERIC AND PLANETARY SCIENCES IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE IN EARTH AND PLANETARY SCIENCES at the UILJh MASSACHUSETTS INSTITUTE OF TECHNOLOGY SEPTEMBER 2013 ©2013 Massachusetts Institute of Technology. All rights reserved. Signature of Author: Depart ef Earth, At eric and P anetary Science August 26 13 Certified by: (3 Roger E. Summons Professor of Geobiology Thesis Supervisor Accepted by: Robert van der Hilst Department Head of Earth, Atmospheric and Planetary Sciences and Schlumberger Professor of Geophysics 1 This page intentionally left blank. 2 Establishing Geochemical Constraints on Mass Accumulation Rates Across the Cretaceous-Paleogene Boundary With Extraterrestrial Helium-3 by Marie Minh-Thu Giron Submitted to the Department of Earth, Atmospheric and Planetary Sciences on August 26, 2013 in Partial Fulfillment of the Requirements for the Degree of Master of Science in Earth, Atmospheric and Planetary Sciences Abstract Records of ocean biogeochemistry in marine sediments show shifts across the Cretaceous-Paleogene boundary (K-Pg) that are simultaneous with the extinction event and onset of the boundary clay deposition. However, the timescale of these records is difficult to determine near the boundary because of fluctuating sedimentation rates and the short duration of the event. In this study, we have used extraterrestrial helium-3 as a constant flux proxy for instantaneous mass accumulation rates in four marine sections: Caravaca, Spain; El Kef, Tunisia; and Hojerup and Kulstirenden, Denmark. These sections are characterized by a thick boundary clay layer and, therefore, are more suitable than many other proxies for high-resolutions studies. In order to better understand the extent of the impact-related perturbations in different paleoenvironments, we performed a high-resolution analysis at Caravaca and lower-resolution analyses at the other three sections. We find that Hojerup and Kulstirenden are not suitable for this analysis due to the probable variation in the flux of extraterrestrial helium-3 as a result of lateral changes in sedimentation rate. Our results suggest that carbonate burial, and likely carbonate production, were more severely affected with increasing paleolatitude. However, the unique depositional environments are probably much more important than just paleolatitude alone. We calculate boundary clay durations of Caravaca and El Kef of 6.45 (h 0.86) kyr and 6.28 (± 1.03) kyr, respectively. These results are consistent with other studies and indicate a uniform, global deposition of the boundary clay and a rapid recovery of carbonate burial in the marine ecosystem after the Cretaceous-Paleogene extinction event. Thesis Supervisor: Roger E. Summons Title: Professor of Geobiology 3 This page intentionally left blank. 4 Acknowledgements There are many people whom I need to thank for contributing to my growth as a scientist and engaged citizen of the world. I would first like to thank my thesis supervisor, Roger Summons, for giving me the opportunity to study at such a unique and stimulating institution. I learned a great deal working in E25, and the lessons learned are not limited to the earth sciences. I am grateful to my mentor, Julio Sepinlveda, for introducing me to the wonderful world of the Cretaceous-Paleogene and patiently supporting and teaching me. I am extremely thankful for the experiences I had in the field in Tunisia and Spain that he made happen. I thank Sujoy Mukhopadhyay for advising me on this project, analyzing my samples, and allowing me to expand my skill set. I would also like to thank David McGee for being available as a resource and providing useful feedback. I can say without a doubt that this thesis would not have been completed on time without the support of my thesis-writing buddies, Sara Lincoln and Alex Evans. I am eternally grateful that Sara has been my mentor, advocate, big sister, and friend, and I cannot imagine having gone through this experience without her. I am thankful to Alex introducing me to the MIT Graduate Student Council, an experience that has changed my career plans if not my life. I thank him for showing me what true productivity and hard work look like and for working by my side during the daytime and occasionally through the night. I thank my Graduate Student Council family for opening my eyes to the fulfillment that results from passion and service. My experience serving on the GSC lit a fire in me, and I hope that fire never dies. I especially thank my Activities Co-Chair, Alex Guo, for being a friend and sister. I have never enjoyed working with a partner so much, and I hope this is not the end of our partnership. I am lucky to have such wonderful friends, and I thank all of them for making me smile and take a break from perfecting my stress lines. I thank my roommates, Cristina Camayd, Michelle Lira, and Monika Avello for their patience, love, and support. I thank Bomy Lee Chung, Angela Laurance, Florence Schubotz, Helen Feng, Sharon Newman, Ross Williams, Yodit Tewelde, and Ruel Jerry for being great friends, especially during stressful times. I finally thank my family for their support and unconditional love. 5 This page intentionally left blank. 6 Table of Contents Chapter 1: Introduction.............................................................................................. 9 Cretaceous-Paleogene M ass Extinction.................................................................. 9 M arine Ecosystem Recovery .................................................................................... 12 Outline of Thesis................................................................................................... 14 Chapter 2: Analytical Background........................................................................... 15 Extraterrestrial Helium -3 ....................................................................................... 15 A pplication of the Extraterrestrial Helium -3 Proxy.............................................. 18 Chapter 3: Experime ntal Procedures. ..................................................................... 21 Sam ple Background............................................................................................... 21 Sam ple Preparation.............................................................................................. 23 H elium A nalysis................................................................................................... 24 Chapter 4: Cretaceous-PaleogeneS ections ............................................................. 27 Caravaca, Spain......................................................................................................... 28 El Kef, Tunisia ................................................ 30 Stevns K lint, D enm ark.......................................................................................... 32 Chapter5 : Results and D iscussion.......................................................................... 37 Caravaca, Spain......................................................................................................... 41 El Kef, Tunisia ................................................ 46 H ojerup, D enm ark................................................................................................. 50 Ku lstirenden, D enm ark .......................................................................................... 52 Conclusion. ................................................................................................................... 65 References..................................................................................................................... 67 Appendix ....................................................................................................................... 73 7 This page intentionally left blank. 8 Chapter 1: Introduction Cretaceous-PaleogeneM ass Extinction The Cretaceous-Paleogene (K-Pg) mass extinction event is the most recent of Earth's 'big five' Phanerozoic mass extinction events and occurred 66 million years ago (Figure 1) [1-3]. Evidence for the global K-Pg extinction event is clearly seen in the fossil record with the disappearance of Mesozoic species and the appearance of Cenozoic species, and it is estimated that at least 60% of all species went extinct within just a few million years [4]. Groups that underwent severe extinction include calcareous nannoplankton [5], planktic foraminifera [6], and dinosaurs [7]. This mass extinction was a critical event in the history of the Earth and changed the course of biological evolution. The most significant trigger of the extinction is widely accepted to be a bolide impact that struck near the present day Yucatan Peninsula and formed the Chicxulub Crater (Figure 2) [4, 8]. Evidence for this catastrophic and contemporaneous impact is seen worldwide in marine sediments and includes the famous iridium anomaly discovered by Alvarez et al. [9]. The presence of ejecta spherules, Ni-rich spinels, and shocked minerals also support an extraterrestrial impact, and they are found in the highest concentrations nearest the Chicxulub Crater [4]. The prolonged eruption of the Deccan Traps in India and the resulting environmental effects may have also contributed to the mass extinction [10]. The extraterrestrial impact had global effects, the most immediate of which was the injection of dust and aerosols into the atmosphere [11]. The impact ejecta and the sulfur aerosols formed from volatilization of impacted anhydrite deposits 9 600 J 550 Late Ashgillian Djhulfian 5 Maastrichtian 0 Sooo L (end Ordovician) (end Permian) (end Cretaceous) 4500 W- 2 Late Frasnian 4 Late Norian 400 (Late Devonian) (end Triassic) C 0 2 50 0~)2 0250 o IA 0 1500 L EL A B M[ 100 0 1 1 ~ ~ S0 01~~~ - - . . 0-- Ord S Dev Carb Perm Tri Jur Cret Pgn N ~ 0 o o q 0 ~ 0 t 0 00* 0Q 0 0 tO'*-0 0 0 N q# ~ C~30) C (0 0 N N N N 01- - - Millions of Years Ago Figure 1. Diversity throughout the Phanerozoic. Arrows point to the 'big five' mass depletions and extinctions. Figure taken from Bambach et al., 2004 [12]. drastically reduced the intensity of solar insolation at the Earth's surface [11]. This resulted in a transient devastation to primary productivity [11] and possible nutrient scarcity at higher trophic levels [13], although this continues to be much debated [14]. Another proposed factor that contributed to decreased insolation was soot produced by widespread wildfires [15]. The resulting 'nuclear winter' caused short-lived cooling [16], contributing to ecosystem instability. Another proposed effect of the impact was acid rain resulting from the regional production of nitrous and nitric acid by both heating of the atmosphere [17] and wildfires [18] and from the production of sulfuric acid from the sulfate aerosols mentioned above [11]. Local weathering [17] and surface ocean acidification [14] may have increased as a result of the acid rain, making some environments toxic. The immediate effects of the 10
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