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Bio/Organic Compound Detection Using Sodium Sulfate Minerals: Implications in the Search for Life on Mars and Europa

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Bio/Organic Compound Detection Using Sodium Sulfate Minerals: Implications in the Search for Life on Mars and Europa University of Montana ScholarWorks at University of Montana Graduate Student Theses, Dissertations, & Professional Papers Graduate School 2010 BIO/ORGANIC COMPOUND DETECTION USING SODIUM SULFATE MINERALS: IMPLICATIONS IN THE SEARCH FOR LIFE ON MARS AND EUROPA Charles Doc Richardson 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 Richardson, Charles Doc, "BIO/ORGANIC COMPOUND DETECTION USING SODIUM SULFATE MINERALS: IMPLICATIONS IN THE SEARCH FOR LIFE ON MARS AND EUROPA" (2010). Graduate Student Theses, Dissertations, & Professional Papers. 1311. https://scholarworks.umt.edu/etd/1311 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]. BIO/ORGANIC COMPOUND DETECTION USING SODIUM SULFATE MINERALS: IMPLICATIONS IN THE SEARCH FOR LIFE ON MARS AND EUROPA By: CHARLES DOC RICHARDSON Bachelor of Science Geosciences, University of Colorado, Boulder, CO, 2001 Master of Science Geosciences, University of Otago, Dunedin, New Zealand, 2003 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- December 2009 Approved by: Perry Brown, Associate Provost for Graduate Education Graduate School Nancy Hinman, Chair Geosciences Jill Scott, Chemical Sciences, Idaho National Laboratory Julia Baldwin Geosciences James Sears Geosciences Michael DeGrandpre Chemistry Carrine Blank Geosciences Richardson, C. Doc, Ph.D., Fall 2009 Geosciences Bio/organic compound detection using sodium sulfate minerals: implications in the search for life on Mars and Europa Chair: Nancy Hinman ABSTRACT With the discovery of Na-sulfate minerals (thenardite, mirabilite) on Mars and Europa, recent studies using these minerals have focused on their ability to assist in the detection of biosignatures. On Earth, biotic and biotic processes can assist in the formation and deposition of these minerals. A primary objective of these studies is the detection of bio/organic compounds that may be associated with the mineral. These biosignatures would imply biological involvement during mineral formation. The following research presents a series of natural and synthetic investigations to determine if biological activity is associated with Na-sulfate mineralization, and if these minerals can assist in detecting bio/organic compounds. Evidence for biological activity associated with the formation of Na-sulfate deposits in the basaltic subsurface of Craters of the Moon National Monument, Idaho was examined by laser desorption Fourier transform mass spectrometry (LD-FTMS), infrared spectroscopy and sulfur isotopic fractionation. These experiments show that bio/organic compounds are likely associated with the secondary Na-sulfate minerals, suggesting biological involvement in the mineralization of these deposits. LD-FTMS results of the synthetic bio/organic-mineral combinations show the potential of Na-sulfate minerals to assist in the detection and identification of bio/organic compounds. These results prove the importance of Na-sulfate minerals for future exploration missions that are likely to use LDMS to search for signs of life in the solar system. ii ACKNOWLEDGEMENTS Doc wants to thank YOU!! iii PREFACE The following dissertation discussion is based on my doctoral research conducted between 2005 and 2009 in the Geosciences Department at the University of Montana- Missoula. This discussion focuses on the effectiveness of thenardite (Na2SO4) to assist in the desorption and identification of various types of bio/organic compounds. Bio/organic compounds are defined as chemical compounds produced by living organisms or derived from other biogenic organic compounds. These observations underpin the determination of bio/organic compounds are associated with secondary mineralization at Craters of the Moon National Monument, Idaho (COM). The following chapters are arranged to follow this progression. Chapter 1 is a basic introductory chapter that provides the necessary knowledge about thenardite formation on Earth and the solar system. Additionally, it reviews the methodology and rationale behind the laser desorption-Fourier transform mass spectrometry (LD-FTMS) instrument. The chapter also discusses pertinent background information that may not be covered in the subsequent research chapters. Chapter 2 was published in the journal Geomicrobiology in August 2008. Its focus is to determine the effectiveness of thenardite in the detection of aliphatic fatty acids, in addition to discovering the limit of detection of the LD-FTMS instrument. Chapter 3 focuses on the identification, formational mechanisms and gas-phase reactions of aromatic amino acids associated with thenardite, it was accepted by the International Journal of Astrobiology in July 2009. The following two chapters focus on the secondary mineralization at COM. Chapter 4 uses X-ray powder diffraction, attenuated total reflectance-Fourier transform infrared spectroscopy, and LD-FTMS to identify and characterize the secondary deposits found in the subsurface of COM. In addition, the iv chapter introduces the COM basalts as a viable analog to martian basalts. It is currently under review by the journal of Chemical Geology. Subsequently, chapter 5 discusses the role of microbial activity in the formation of thenardite in the secondary deposits at COM. It is currently in review by the journal of Earth and Planetary Science Letters. Finally, the last chapter offers a quick summary of the overall results of this dissertation research and discusses its implications into the search for life in the solar system. With the exception of chapter 1, all the chapters were submitted for publication and are still formatted to reflect their respective journal. Thus each chapter has its own reference list and any redundancy in the introduction and methodology between these chapters is inescapable. Fortunately, the numbering of the tables and figures has been changed to reflect this discussion. Appendix 1 is an excerpt from a recently published review chapter that discusses the occurrence and fate of organic compound in the solar system. The chapter title is called, “The stellar stew: Distribution of extraterrestrial organics in the universe”. It is in the book “Astrobiology: from simple molecules to primitive life”, published by American Scientific Publishers. v TABLE OF CONTENTS ABSTRACT ...................................................................................................................... ii ACKNOWLEDGEMENTS .................................................................................................. iii PREFACE ........................................................................................................................ iv TABLE OF CONTENTS ..................................................................................................... vi TABLE OF FIGURES ..........................................................................................................x TABLE OF TABLES .......................................................................................................... xi CHAPTER 1: INTRODUCTION .........................................................................................1 1.1. OVERVIEW ...............................................................................................................1 1.2. OCCURRENCE OF TERRESTRIAL NA-SULFATE MINERALS .........................................3 1.2.1. Evaporitic Settings ...........................................................................................3 1.2.2. Craters of the Moon National Monument ........................................................4 1.3. OCCURRENCE OF NA-SULFATE MINERALS IN THE SOLAR SYSTEM ..........................7 1.3.1. Io ......................................................................................................................7 1.3.2. Ganymede ........................................................................................................8 1.3.3. Formation and Emplacement of Na-sulfate Minerals on Europa ....................8 1.3.4. Formation of Secondary Na-sulfate Minerals on Mars..................................10 1.4. ORGANIC COMPOUNDS AND PATHWAYS OF BIO/ORGANIC COMPOUNDS ...............14 1.4.1. Chemical Pathways of Bio/organic Compounds on Europa ..........................14 1.4.2. Chemical Pathways and Preservation of Bio/organic Compounds on Mars .18 1.5. ORGANIC COMPOUNDS AND THEIR RELATIONSHIP TO BIOTIC AND ABIOTIC PROCESSES.............................................................................................................21 1.6. BACKGROUND OF GEOMATRIX-ASSISTED LASER DESORPTION/IONIZATION FOURIER TRANSFORM ION CYCLOTRON RESONANCE MASS SPECTROMETRY ........24 1.7. REFERENCES ..........................................................................................................27 CHAPTER 2: EXPLORING BIOSIGNATURES ASSOCIATED WITH THENARDITE BY GEOMATRIX-ASSISTED LASER DESORPTION/IONIZATION FOURIER TRANSFORM ION CYCLOTRON RESONANCE MASS SPECTROMETRY (GALDI-FTICR-MS) ........37 vi 2.1. ABSTRACT ..............................................................................................................37
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