Amino Acid Synthesis in Meteoritic Parent Bodies of Carbonaceous Chondrites Amino Acid Synthesis in Meteoritic Parent Bodies of Carbonaceous Chondrites By Alyssa Cobb, B.Sc. A Thesis Submitted to the School of Graduate Studies in Partial Fulfilment of the Requirements for the Degree Master of Science McMaster University (cid:13)c Copyright by Alyssa Cobb, August 2013 Master of Science (2013) McMaster University (Physics and Astronomy) (Collaborative Graduate Program in Astrobiology) Hamilton, Ontario TITLE: Amino Acid Synthesis in Meteoritic Parent Bodies of Carbonaceous Chondrites AUTHOR: Alyssa Cobb, B.Sc. (Colorado School of Mines) SUPERVISOR: Ralph E. Pudritz NUMBER OF PAGES: xv, 119 ii Abstract The class of meteorites called carbonaceous chondrites are examples of material from the solar system which have been relatively unchanged from the time of their initial formation. We investigate the carbonaceous chondrite subclasses CI, CM, CR, CV, and CO, which contain high levels of water and organic material, including amino acids. These subclasses span petrologic types 1 through 3, indicating the degree of internal chemistry undergone by the meteoritic parent body. The goal of this thesis is two-fold: to obtain a comprehensive view of amino acid abundances and relative frequencies in carbonaceous chondrites, and to recreate these patterns via thermodynamic computational models. We collate available amino acid abundance data for a variety of meteorites to identify patterns in total abundance and relative frequencies. We consider only a set of 20 proteinogenic α-amino acids created via a specific chemical pathway called Strecker synthesis. We plot abundances of individual amino acids for each subclass, as well as total abundances across all subclasses. We see a predominance in abundance and variety of amino acids in the CM and CR subclasses, which contain concentra- tions of amino acids greater by several orders of magnitude than other carbonaceous subclasses. These subclasses correspond to an aqueous alteration temperature range of 200◦C to 400◦C. Within the CM2 and CR2 meteorites, we identify trends in the relative frequencies of amino acids in preparation for computational modeling. Now having a baseline observed amino acid abundance plot, we recreate both the total amino acid abundance pattern as well as the relative frequency of amino acids within the CM2 chondrite subclass using computational models. We use thermo- dynamic theory of Gibbs free energies to calculate the output of amino acids in a meteoritic parent body assuming chemical equilibrium and some set of initial con- iii centrations of organic material. Our model recreates abundance patterns in the tem- perature range 200◦C to 400◦C, ∼ 105 parts-per billion (ppb), and the temperature range 400◦C to 500◦C, ∼ 102 ppb. Our model does not fit well between tempera- tures of 150◦C to 200◦C. Our current model assumes a uniform composition of initial chemical reactants; likely an inhomogeneous composition would be a more accurate physical representation of a parent body. In addition, we match relative frequencies to observed frequencies for each amino acid in the CM2 subclass to well within an order of magnitude. iv Acknowledgements This project represents two years’ worth of effort and hard work. It would never have come to pass without the assistance of many people, I am especially grateful to my super- visor, Prof. Ralph Pudritz, for his direction and myriad suggestions regarding the greater context of this project in the fields of astrobiology and astrophysics. Thanks also my com- mittee members Prof. Doug Welch and Prof. Greg Slater. Much of this research has benefited from the experience of, and/or discussion with, a variety of people. The crowd at NASA Goddard has been an invaluable reference, especially regarding amino acid abundances in meteorites, including Daniel Glavin, Aaron Burton, and Jamie Elsila. Thanks also to Stephen Freeland, at University of Hawai’i, and Jason Hein, at University of California, Merced. We also received assistance from people closer to home. Prof. Paul Ayers, at McMaster University, helped immensely with his expertise in theoretical chemistry. His graduate student, Farnaz Zadeh. Also Darren Fernandes and Lee Bardon, both summer research students who worked on this project with me, and Jeff Emberson, who began the project with Ralph before I arrived. I am also indebted to the Canadian Astrobiology Training Program for the graduate fellowship on which I depend. I am very grateful to my fellow graduate students Mikhail Klassen and Rory Woods for their regular assistance and expertise in Python and coding in general. For all the late nights, early mornings, and sweaty afternoons, thank you to the whiskey, pancake, and softball crowds. You guys made this a lot of fun and more bearable than it otherwise might have been. I was being extremely clever and you guys were excellent at standing around looking impressed! And finally, to my family. The love and encouragement of my parents have followed me across continents and fields of study. I know their unconditional support will continue with whatever I chose to do next. v Dedicated to Disney & The Doctor vi Table of Contents Descriptive Notes ii Abstract iii Acknowledgements v List of Figures x List of Tables xiv Chapter 1 Introduction 1 Chapter 2 Background 5 2.1 Observational Background . . . . . . . . . . . . . . . . . . . . . . . . 5 2.2 Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 2.2.1 Proteinogenic α-Amino Acids . . . . . . . . . . . . . . . . . . 10 2.2.2 Parent Body Processes: Strecker Synthesis . . . . . . . . . . . 11 2.2.3 Strecker Reactions for Proteinogenic Amino Acids . . . . . . . 16 2.2.4 Initial Concentrations of Organics . . . . . . . . . . . . . . . . 20 2.3 Computations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 2.3.1 Gibbs Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 2.3.2 CHNOSZ and Gibbs Energy Coefficients . . . . . . . . . . . . 25 2.3.3 CHNOSZ Ancestor . . . . . . . . . . . . . . . . . . . . . . . . 26 vii Chapter 3 Nature’s Starships I: Abundance and Relative Frequency of Amino Acids in Meteorites 31 Abstract 32 3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33 3.2 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36 3.2.1 Amino Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . 36 3.2.2 Meteoritic Classification . . . . . . . . . . . . . . . . . . . . . 38 3.3 Materials and Methods . . . . . . . . . . . . . . . . . . . . . . . . . . 41 3.3.1 Meteoritic Amino Acid Data . . . . . . . . . . . . . . . . . . . 41 3.4 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51 3.4.1 Amino Acid Abundance Patterns . . . . . . . . . . . . . . . . 53 3.4.2 Normalized Amino Acid Relative Frequencies . . . . . . . . . 55 3.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58 3.6 Supplementary Material . . . . . . . . . . . . . . . . . . . . . . . . . 60 3.6.1 Amino Acid Data . . . . . . . . . . . . . . . . . . . . . . . . . 60 3.6.2 Note on Relative Frequencies . . . . . . . . . . . . . . . . . . 69 Chapter 4 Nature’s Starships II: Computational Modeling of Amino Acid Synthesis in Meteoritic Parent Bodies of Carbonaceous Chondrites 73 Abstract 74 4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76 viii
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