University of Montana ScholarWorks at University of Montana Graduate Student Theses, Dissertations, & Professional Papers Graduate School 2009 Biosignature storage in sulfate minerals- synthetic and natural investigations of the jarosite group minerals Julia Michelle Kotler The University of Montana Follow this and additional works at: https://scholarworks.umt.edu/etd Let us know how access to this document benefits ou.y Recommended Citation Kotler, Julia Michelle, "Biosignature storage in sulfate minerals- synthetic and natural investigations of the jarosite group minerals" (2009). Graduate Student Theses, Dissertations, & Professional Papers. 1275. https://scholarworks.umt.edu/etd/1275 This Dissertation is brought to you for free and open access by the Graduate School at ScholarWorks at University of Montana. It has been accepted for inclusion in Graduate Student Theses, Dissertations, & Professional Papers by an authorized administrator of ScholarWorks at University of Montana. For more information, please contact [email protected]. BIOSIGNATURE STORAGE IN SULFATE MINERALS- SYNTHETIC AND NATURAL INVESTIGATIONS OF THE JAROSITE GROUP MINERALS By JULIA MICHELLE KOTLER Bachelor of Science Chemistry, University of Montana, Missoula, Montana, 2004 Dissertation presented in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Geosciences The University of Montana Missoula, MT Official Graduation Date - July 2009 Approved by: Perry Brown, Associate Provost for Graduate Education Graduate School Nancy Hinman, Chair Geosciences Julia Baldwin Geosciences Steven Sheriff Geosciences James Sears Geosciences Edward Rosenberg Chemistry Jill Scott Chemical Sciences, Idaho National Laboratory Kotler, Julia M., Ph.D., Spring 2009 Geosciences Biosignature storage in sulfate minerals- synthetic and natural investigations of the jarosite group minerals Chairperson: Nancy Hinman ABSTRACT The discovery of jarosite on Mars in 2004 generated increased interest in the properties of the mineral related to the search for life on other planets. Several studies indicate that the formation of jarosite can be linked to biological activity on Earth and biomolecules such as amino acids have been found associated with terrestrial jarosite samples. A series of natural and synthetic investigations using different jarosite end- members has been conducted and is presented in this dissertation to investigate the possibility that jarosite can store biosignatures. Natural samples were analyzed by X-ray diffraction, elemental carbon analysis and laser-desorption Fourier transform mass spectrometry (LD-FTMS) and were found to contain the amino acid glycine. Synthetic experiments were conducted in which the different end-members were synthesized in the presence of glycine as well as the amino acid alanine and the amino acid breakdown product methylamine. These samples were analyzed by X-ray diffraction, neutron diffraction, LD-FTMS and thermogravimetric analysis (TGA) techniques. Results of these experiments show that the detection of the biosignature and the effect that biomolecule has on the jarosite minerals is dependent on the end-member and indicate that the jarosite minerals are an excellent target for detecting potential signs of past life on other planets. ii ACKNOWLEDGEMENTS So many people have contributed both personally and scientifically to this project over the years. Every time I thought I couldn’t continue, someone was there to help me find a way to push forward. To everyone who had to listen to endless hours of discussion about jarosite or the latest theories about Mars, I thank you. I thank you for the support, encouragement and even the blank stares. Sometimes all I needed was someone to listen. I would like to thank my family, my friends, my dissertation committee, and all of the colleagues I have worked with over the years who have helped me make this possible. I would like to thank the three most influential scientists in my life, Dr. Kent Sugden, Dr. Nancy Hinman, and Dr. Jill Scott for giving me the foundation in which to build this project and achieve success. Kent’s influence still holds today, many years later, as I remember the things he taught me in my early days of research. Nancy’s support has been unyielding, and I couldn’t imagine a better person to have spent time with both in the field and in the laboratory. She has given me so many opportunities to succeed and grow as a scientist. Lastly, to Jill, you have always found a way to help me stand up again no matter how many times I would fall down. Your patience has never gone unnoticed or unappreciated. I would like to dedicate this dissertation to my grandmother, Patricia Brigati. Had she not been willing to take a chance on me so many years ago when she co-signed my first student loan, none of this would have possible. Thanks G! Thanks for believing in me and enduring the harassment from Wells Fargo. iii PREFACE This dissertation represents the final research work for my Ph.D conducted from 2004 – 2009 at the University of Montana Geosciences Department. What follows are five chapters and two appendices. Chapter 1 provides a general introduction to the subjects covered within the research chapters including; background information on the formation of the jarosite minerals on Earth and Mars, extraterrestrial amino acids, jarosite chemistry and crystallography, and an overview of techniques used that are less common in the geosciences. Chapter 2 is a research chapter that was published in the journal Astrobiology in April 2008. Chapter 2 covers X-ray diffraction, carbon elemental analysis, and Laser Desorption- Fourier Transform Mass Spectrometry (LD-FTMS) analysis conducted on natural samples of jarosite from various locations around the world in which the amino acid glycine was found associated with the mineral samples. Chapter 3 is a research chapter that was accepted for publication in the journal Planetary and Space Science in June of 2009. This chapter represents of a series of synthetic experiments with several jarosite end-members that were synthesized in the presence of glycine and then analyzed by thermal gravimetric analysis (TGA) techniques. Chapter 4 is a research chapter that was submitted to the Journal of Thermal Analysis and Calorimetry that was accepted July 2009. The chapter presents the results of jarosite end- members synthesized in the presence of the amino acid alanine and the amino acid degradation product methylamine studied by TGA. Chapter 5 is the last research chapter and represents X-ray and neutron diffraction studies of jarosite end-members synthesized in the presence of glycine. iv Appendix 1 is a review chapter titled “The Stellar Stew: Distribution of Extraterrestrial Organics in the Universe”. It was accepted for publication in August of 2008 in the book “Astrobiology: from simple molecules to primitive life” published by American Scientific Publishers. This chapter reviews current literature related to the formation and detection of organic molecules in the universe including the interstellar medium, interplanetary dust particles, asteroids/chondritic meteorites and comets, planetary bodies and meteorites. Appendix 2 is a research chapter that covers some of the initial X-ray and LD-FTMS studies of the synthetic jarosite samples that provided the groundwork for the later research chapters. Since many of the chapters were submitted as manuscripts, the formatting for those chapters remained similar to the journal format with the exception of header, figure and table numbering. As a consequence of this, each of the chapters has its own reference section and an amount of redundancy within the introductions of those chapters was unavoidable. v ABSTRACT……………………………………………………………………………...ii ACKNOWLEDGEMENT…………………………………………………………...…iii PREFACE……………………………………………………………………………….iv TABLE OF FIGURES………………………………………………………………….ix TABLE OF TABLES…………………………………...……………………………....xi CHAPTER 1: INTRODUCTION ................................................................................... 1 1.1 GENERAL INTRODUCTION ........................................................................................................ 1 1.2 FORMATION OF JAROSITE MINERALS ON EARTH AND MARS .............................. 3 1.3 ROLE OF SULFUR IN SHAPING THE MARTIAN SURFACE ..................................................... 6 1.4 EXTRATERRESTRIAL AMINO ACIDS ..........................................................................................14 1.5 JAROSITE CHEMISTRY AND CRYSTALLOGRAPHY ...............................................................23 1.6 OVERVIEW OF TECHNIQUES ........................................................................................................29 1.6.2 DETECTION OF BIOSIGNATURES BY GEOMATRIX-ASSISTED LASER DESORPTION/IONIZATION (GALDI) MASS SPECTROMETRY .....................................................30 1.6.3 POWDER DIFFRACTION STRUCTURE SOLUTION METHODS ............................................32 1.7 REFERENCES ......................................................................................................................................39 CHAPTER 2: GLYCINE IDENTIFICATION IN NATURAL JAROSITES USING LASER DESORPTION FOURIER TRANSFORM MASS SPECTROMETRY: IMPLICATIONS FOR THE SEARCH FOR LIFE ON MARS ................................ 51 2.1 ABSTRACT ...........................................................................................................................................51 2.2 INTRODUCTION