Formation of Iron-Rimmed Sandstone Nodules on Earth; Terrestrial Analogue for the Formation of Martian Blueberries?

Scholars' Mine Masters Theses Student Theses and Dissertations Fall 2009 Formation of iron-rimmed sandstone nodules on earth; terrestrial analogue for the formation of Martian blueberries? Katherine Charlotte Muller Follow this and additional works at: https://scholarsmine.mst.edu/masters_theses Part of the Geology Commons Department: Recommended Citation Muller, Katherine Charlotte, "Formation of iron-rimmed sandstone nodules on earth; terrestrial analogue for the formation of Martian blueberries?" (2009). Masters Theses. 4727. https://scholarsmine.mst.edu/masters_theses/4727 This thesis is brought to you by Scholars' Mine, a service of the Missouri S&T Library and Learning Resources. This work is protected by U. S. Copyright Law. Unauthorized use including reproduction for redistribution requires the permission of the copyright holder. For more information, please contact [email protected]. i FORMATION OF IRON-RIMMED SANDSTONE NODULES ON EARTH; TERRESTRIAL ANALOGUE FOR THE FORMATION OF MARTIAN BLUEBERRIES? by KATHERINE CHARLOTTE MULLER A THESIS Presented to the Faculty of the Graduate School of the MISSOURI UNIVERSITY OF SCIENCE AND TECHNOLOGY In Partial Fulfillment of the Requirements for the Degree MASTER OF SCIENCE IN GEOLOGY 2009 Approved by David J. Wronkiewicz – Advisor John P. Hogan Melanie R. Mormile ii 2009 Katherine Charlotte Muller All Rights Reserved iii ABSTRACT NASA’s twin Mars Exploration Rovers, MER, Spirit and Opportunity, have identified numerous geologic features that hint at a watery past on Mars noted in Malik, 2004. Prominent among these features are the “Martian Blueberries” that occur as spherical hematite (Fe 2O3) nodules. Hematite formation is facilitated by the presence of water, although there are presently no known sources of free liquid water on Mars. Chan et al., 2004 states that these “blueberries” are also similar to nodules found in the Jurassic aged Navajo Sandstone in Utah. An understanding of the processes controlling the formation of the Utah nodules may thus be key in determining the processes of nodule formation on Mars. A ferrous ammonium sulfate leachant solution (pH ≈ 4.5) was reacted with various mineral phases in a static batch test to induce pH and/or Eh changes that could cause a decrease in iron solubility. Following the static batch tests, flow-through tests were conducted exposing columns with loose packed quartz sand and isolated crystals of calcite and epsomite to a solution containing ferrous ammonium sulfate at a slow flow rate. Two more flow tests were completed using mechanically rounded samples of calcite cemented Dakota Sandstone. Finally, a reaction chamber was designed using inert gasses, argon and nitrogen, to examine the reaction sequence in an anoxic environment. The conclusions of the previously mentioned tests demonstrated that carbonate minerals induced a pH increase, which in turn induced the precipitation of iron oxide that mimicked the shape of the grains. The Dakota sandstone drip tests both produced halos around the surface of the samples. iv ACKNOWLEDGEMENTS This research project would not have been possible without the support of many people. I wish to express my gratitude to my advisor, Dr. Wronkiewicz, who was abundantly helpful and offered assistance and guidance. Deepest gratitude is also due to the members of the thesis committee, Dr. Hogan and Dr. Mormile, without whose knowledge and assistance this study would not have been successful. I would also like to convey thanks to the University and Geology Department for providing the financial means and laboratory facilities. I am tempted to individually thank all of my friends but because the list might be too long, I will simply say thank you very much to you all. I wish to express my gratitude to my family; for their understanding and endless love, through the duration of my studies. I wish to thank my parents, Robert and Christina Downs, and my husband, Ian Muller. They have supported and encouraged me to always do my best. To them I dedicate this thesis. v TABLE OF CONTENTS Page ABSTRACT……………………………………………………………………………...iii ACKNOWLEDGEMENTS………………………………………………………………iv LIST OF ILLUSTRATIONS……………………………………………………….........vii LIST OF TABLES…………………………………………………………………..........ix SECTION 1. INTRODUCTION….……………………………………………………………….1 1.1 GENERAL STATEMENT………………………………….………………......1 1.2 MOQUI MARBLE VS. MARTIAN BLUEBERRIES.…………………………1 1.3 SIGNIFICANCE OF MARTIAN BLUEBERRIES…….……………………....2 1.4 PURPOSE STATEMENT……………………………….……………………...3 2. GEOLOGIC BACKGROUND……………………………………………………...4 2.1 MARS...........................................................................................................…....4 2.2 MARTIAN BLUEBERRIES……………………………………………....……6 2.3 MOQUI MARBLES……………………………………………………....…….7 2.4 NAVAJO SANDSTONE..............................................................................…....9 2.5 ST. PETER SANDSTONE……………………………………………....…….10 3. METHODS………………………………………………………………………...12 3.1 GENERAL INFORMATION……………………………………………….....12 3.2 STATIC BATCH TESTS WITH CALCITE, EPSOMITE, GYPSUM, MAGNESITE, AND SIDERITE.........................................................................14 3.3 STATIC BATCH TEST - WITH BASALT........................................................16 3.4 DRIP TESTS.......................................................................................................18 3.5 SCANNING ELECTRON MICROSCOPY (SEM) EXAMINATION OF SAMPLES…..…………………......……….…...….…..24 3.6 NITROGEN AND ARGON ATMOSPHERE DRIP TESTS...…….………….26 3.7 INDUCTIVELY COUPLED PLASMA – OPTICAL EMISSION SPECTROMETER (ICP-OES)...........................................................................33 4. RESULTS…………………………………………………………………………..35 vi 4.1 STATIC BATCH TESTS USING CALCITE, GYPSUM, MAGNESITE, OR SIDERITE AS AN IRON OXIDE PRECIPITANT…....…..………….……….35 4.2 STATIC BATCH TEST USING BASALT AS AN IRON OXIDE PRECIPITANT……...…….......………….……………………………40 4.3 DRIP TEST WITH CALCITE…………....….…………………………………43 4.4 DRIP TEST WITH DAKOTA SANDSTONE SAMPLES.................................45 4.5 SCANNING ELECTRON MICROSCOPY (SEM) ANALYSIS........................49 4.6 CONTROLLED ATMOSPHERE DRIP TEST...................................................58 4.7 ANALYSIS OF SOLUTION SAMPLES……………………………….……...69 5. DISCUSSION……………………………………………………………………....70 5.1 STATIC BATCH TESTS……….....…………………………………………...70 5.2 DRIP TESTS………....………………………………………………………....72 5.3 ANALYSIS OF SAMPLES AND EDS SPECTRA……………………....…....74 5.4 CONTROLLED ENVIRONMENT DRIP TEST………………………....……76 5.5 IRON OXIDE CONCENTRATIONS FROM PORTS IN REACTION CHAMBER...……………………………..............……………………........….79 5.6 IRON PRECIPITATION RELATED TO MARS....………........……………...80 6. CONCLUSIONS………………..………………………………………………….82 6.1 LAB SUMMARY…...……………………………………………...…...…......82 6.2 PROJECT SUMMARY……...………………….…………………..................83 BIBLIOGRAPHY……………………………………………………………………85 VITA............................................................................................................................88 vii LIST OF ILLUSTRATIONS Figure Page 1.1 Moqui Marble and Martian Blueberries............................…...…….......................…..2 3.1 Calcite static batch test vessels...................................................................................15 3.2 Charcoal buffer packets...............................................................................................19 3.3 Example of drip test set up..........................................................................................21 3.4 Sand slurry method.....................................................................................................22 3.5 Drip test set up............................................................................................................24 3.6 SEM samples..............................................................................................................25 3.7 Controlled atmosphere column...................................................................................28 3.8 Controlled atmosphere column with argon tank.........................................................29 3.9 Sand core sample extracted from the drip column......................................................32 4.1 Calcite static batch test vessels....................................................................................36 4.2 Eh/pH diagram for calcite and gypsum vessels...........................................................37 4.3 Siderite and magnesite static batch test vessels...........................................................39 4.4 Eh/pH diagram for basalt vessels................................................................................42 4.5 Basalt static batch test vessels.....................................................................................43 4.6 Iron precipitation of calcite grain in column...............................................................44 4.7 Iron coating around calcite grain................................................................................45 4.8 Iron halos around the Dakota sandstone surfaces.......................................................46 4.9 Carbonate halo surrounding Dakota grain..................................................................47 4.10 Specular hematite in Dakota sandstone halo............................................................48 4.11 Results of specular hematite scratch test..................................................................48 4.12 Elmers

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