I Identification and Characterization of Martian Acid-Sulfate Hydrothermal
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Identification and Characterization of Martian Acid-Sulfate Hydrothermal Alteration: An Investigation of Instrumentation Techniques and Geochemical Processes Through Laboratory Experiments and Terrestrial Analog Studies by Sarah Rose Black B.A., State University of New York at Buffalo, 2004 M.S., State University of New York at Buffalo, 2006 A thesis submitted to the Faculty of the Graduate School of the University of Colorado in partial fulfillment of the requirement for the degree of Doctor of Philosophy Department of Geological Sciences 2018 i This thesis entitled: Identification and Characterization of Martian Acid-Sulfate Hydrothermal Alteration: An Investigation of Instrumentation Techniques and Geochemical Processes Through Laboratory Experiments and Terrestrial Analog Studies written by Sarah Rose Black has been approved for the Department of Geological Sciences ______________________________________ Dr. Brian M. Hynek ______________________________________ Dr. Alexis Templeton ______________________________________ Dr. Stephen Mojzsis ______________________________________ Dr. Thomas McCollom ______________________________________ Dr. Raina Gough Date: _________________________ The final copy of this thesis has been examined by the signatories, and we find that both the content and the form meet acceptable presentation standards of scholarly work in the above mentioned discipline. ii Black, Sarah Rose (Ph.D., Geological Sciences) Identification and Characterization of Martian Acid-Sulfate Hydrothermal Alteration: An Investigation of Instrumentation Techniques and Geochemical Processes Through Laboratory Experiments and Terrestrial Analog Studies Thesis directed by Associate Professor Brian M. Hynek Abstract Hydrothermal acid-sulfate alteration is a common process in volcanic systems on Earth, and it may be inferred that this process played an important role in Mars’ geologic history as well. Several areas have been identified on Mars with minerals which are characteristic of acid-sulfate alteration: hydrated silica, sulfates, phyllosilicates, and Fe-oxides. Relic hydrothermal systems will play a key role in future investigations of Mars and the search for biosignatures. It is necessary to develop a detailed understanding of the mineral assemblages which form in these environment, and the geochemical processes by which they arise. This dissertation work addresses our ability to confidently and thoroughly characterize hydrothermal acid-sulfate mineral assemblages using rover-deployed instrumentation methods, and the role of high Fe parent basalts on secondary mineralogy. Analysis of hydrothermal deposits was completed using Mars analog instrumentation to identify strengths and weaknesses for each method. VNIR, XRD, and Raman laser spectrometers analyzed 100 hydrothermally altered terrestrial samples. Results indicate phyllosilicates may be detected in XRD without any additional sample preparation when present at ≥ 10 wt %. VNIR was particularly useful for the identification of phyllosilicates and silica; however, these deposits are easily missed when observed with limited rover VNIR. For more robust phyllosilicate detection iii and “ground truthing” of orbital data, VNIR spectrometers on future rover payloads should cover the entire 300 – 2500 nm range. Previous work has shown that parent rock composition plays a significant role in secondary mineral assemblage, and Icelandic basalts are among the closest terrestrial analogs for Mars. Our examination of the role of primary Fe content on secondary mineralogy found ~60 % Fe natroalunite forming in Iceland, adding to the growing list of natural systems containing intermediate alunite group minerals. There is a direct correlation between parent Fe and the abundance of Fe-bearing secondary minerals. Projected trends from our laboratory investigations indicate 20 – 32 wt % Fe-bearing mineralogy should form in Martian systems, similar to products from our terrestrial basalts. Alteration of crystalline “Mars” basalt produced both Fe-sulfates and Fe-oxides while all others contained only Fe-sulfates, indicating a transition to co-precipitation at > 17.0 wt % parent FeOT. iv Acknowledgements Many thanks to Brian Hynek for his support and making this project possible, as well as the current and former members of the mighty SPACECATS lab, fellow LASP-ians, and friends for their never ending support, encouragement, and laughs: LG Beckerman, John Gemperline, Rachael Hoover, Kara Brugman, Kaitlyn Garifi, Katie Rempfert, Stephanie Junior, Meredith Hazelton, Molly DiCroce, Zarah Brown, Morgan Rehnberg, Marek Slipski, Courtney Peck, Emma Marcucci, Mike Lotto, Will Nelson, Becca Thomas, and Ramy El-Maarry. Numerous people have contributed to my knowledge and growth as a scientist throughout this program, to whom I am extremely grateful: my committee (Alexis Templeton, Tom McCollom, Steve Mojzsis, and Raina Gough), Kathy Kierian-Young, Aileen Yingst and the members of the GHOST team, Matt Chojnacki, Tracy Gregg, Graham Lau, Chris Donaldson, Eric Ellison, Julien Allaz, Jess Larsen, and the truly outstanding CU Boulder geology faculty. And of course, nothing would have been possible without my incredible family: Kathy, Steve, Julie, Dan, and Ryan, and my truly wonderful partner, Jake Aho. Thank you all. I could not have done it without you. Chapters 2 – 4 have been published, submitted, or will soon be submitted in peer-reviewed scientific journals. The acknowledgements for each section are as follows: Chapter 2: This work was funded by a Geological Society of America Graduate Student Research Grant, the Lewis and Clark Fund for Exploration and Field Research in Astrobiology, a NASA Early Career Fellowship to B. M. Hynek, and NASA awards NNX14AN36G and NNX14AG90G. Many thanks to Rebecca Thomas for providing valuable feedback, Kathy Kierian-Young, Emma Marcucci, Kara Brugman, Thomas McCollom, Eric Ellison, LG Beckerman, Rachael Hoover, Stephanie Junior, and Jordan Ludyan for their assistance with v gathering and processing data, and Guillermo Alvarado, and Geoffroy Avard for their assistance in the field. Chapter 3: This work was supported by a Geological Society of America Graduate Student Grant; the American Philosophical Society Lewis and Clark Fund for Exploration and Field Research in Astrobiology, and NASA Habitable Worlds grant NNX15AP15G to LJM and BMH. Many thanks to Jordan Ludyan for assistance with XRF analysis at UWM. Chapter 4: This work was supported by a Geological Society of America Graduate Student Grant; the American Philosophical Society Lewis and Clark Fund for Exploration and Field Research in Astrobiology, and NASA Habitable Worlds grant NNX15AP15G to BMH. Many thanks to Jordan Ludyan for assistance with XRF analysis of parent rocks at UWM. vi Table of Contents 1. Introduction …………………………………………………………………..…………….. 1 1.1. Observation of Mars: A History …………………….……………………..……….….. 2 1.1.1. Telescopic observations ………………………………………………………..… 2 1.1.2. Orbital and in situ spacecraft observations …………………………...………..… 3 1.1.3. Upcoming missions ………………………………………………..…………..… 6 1.2. The geology of Mars ……………………………..……………………...…...………..… 7 1.2.1. A brief geologic history …………..………………………………..…………..… 7 1.2.2. Volcanism and iron-rich basalts ……………….……………………….………… 9 1.2.3. Evidence for surface and subsurface water ………………………..…….……… 11 1.2.3.1. Geomorphological evidence ………………………………………..…….... 11 1.2.3.1.1. Valley networks and deltas ………………………………………..…. 11 1.2.3.1.2. Outflow channels ……………………………………………….....… 12 1.2.3.1.3. Gullies ……………………………………………………………..… 13 1.2.3.2. Mineralogical evidence ………………………………………………….… 13 1.2.3.2.1. Phyllosilicates ……………………………………………………..… 14 1.2.3.2.2. Sulfates …………………………………………………………..…... 15 1.2.3.2.3. Fe-oxides/hydroxides ……………………………………………..…. 16 1.2.3.2.4. Hydrated silica ……………………………………………………..... 17 1.3. Hydrothermal systems on Mars …………..……………………….……..…………… 17 1.3.1. Home Plate, Gusev crater …………………………………………………......… 18 1.3.2. Eastern Coprates Chasma, Valles Marineris ……………………………..…..… 19 1.3.3. Noctis Labyrinthus, Valles Marineris ……………………………….....……..… 19 1.3.4. Cross crater, Terra Sirenum …………………………………………..…..…..… 19 1.3.5. Nili Patera, Syrtis Major ……………………………………………….....…..… 20 1.4. Acid-sulfate alteration: Processes and products ……..……………………...……..… 20 1.5. Dissertation research ………………………………….…………………..…….…..… 22 2. Characterization of terrestrial hydrothermal alteration products with Mars analog instrumentation: Implications for current and future rover investigations …..…..….......... 25 2.1. Introduction ………………………………………………………………….…...…… 25 2.1.1. Hydrothermal alteration on Mars ……………………………………….…..…… 25 2.1.2. Instrumentation ……………………………………………………………......… 28 2.1.2.1. Visible Near-Infrared (VNIR) and Short Wave Infrared (SWIR) Reflectance Spectroscopy ……………………………………………………………………..… 28 2.1.2.2. X-Ray Diffraction (XRD) ………………………………………………..... 32 2.1.2.3. Raman Laser Spectroscopy ………………………………….…………..… 33 2.1.3. Characterization of terrestrial hydrothermal deposits …………………..……...… 35 2.1.4. Field sites ………………………………………………………………...……… 38 2.1.4.1. Poás Volcano, Costa Rica ……………………………………………..…... 40 2.1.4.2. Turrialba Volcano, Costa Rica ………………………………………..…… 41 2.1.4.3. Cerro Negro Volcano, Nicaragua ……………………………………..…… 41 2.1.4.4. Momotombo Volcano, Nicaragua ……………………………….…..…….. 42 2.1.4.5. Telica Volcano, Nicaragua ……………………………………….…..……. 42 2.1.4.6. Krafla Volcano, Iceland ……………………………………………..…….. 43 vii 2.1.4.7. Landmannalaugar Volcano, Iceland …………………………….……..…..