Mars on Discovery and Characterization

Cover Images Top: The Hyper-arid, Mars Analog, Atacama Desert (Chile) with color modifications to appear like a surface image from Mars. Modifications were made with Photoshop by Jacek Weirzchos. Photo Credit: Jacek Weirzchos. Bottom: The surface of Mars. Photo Credit: NASA/JPL.

Mars on Earth: Discovery and Characterization

Methods and technologies to advance the search for sub-surface life.

First Year Report (In Partial Fulfillment of D.Phil Requirements)

Lauren E. Fletcher

Atmospheric, Oceanic, and Planetary Physics University of Oxford Oriel College

Supervisors: Dr. Neil E. Bowles and Dr. Charles Cockell (University of Edinburgh)

Word Count: 15,076 (main text)

August 31, 2011

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Mars on Earth: Discovery and Characterization

Methods and technologies to advance the search for Martian sub-surface life.

Lauren E. Fletcher Oriel College, University of Oxford

First Year Report (In Partial Fulfillment of D.Phil Requirements)

Abstract

The motivation for this project is to try to answer some of mankind‟s most important questions: “Where did we come from?”, “Are we alone in the universe?”, and “What is our future beyond the Earth?” The sub-surface environments of Mars are some of the best places to try to find answers these questions, with the first step to determine if any one location is habitable (or simply that it provides the necessary conditions and resources to support life). A systematic approach to the quantification of the habitability of subsurface environments on Mars is proposed. This will include a series of sensors integrated into a bore-hole device which could be used as part of future drilling missions to Mars.

The work presented in this report starts with a brief overview of previous missions including scientific results relevant to the sub-surface environments of this project and what is missing from these previous missions as well as upcoming missions. This is followed by a discussion of the history of the exploration of Mars prior to the modern space age which provides the fundamental motivation for this project and ends with the establishment of the central hypothesis of the project: The subsurface environment of Mars provides habitable conditions sufficient to support life.

Definitions of the fundamental concepts of Life and Habitable are provided that are used to develop a list of questions that must be answered in order to quantify a habitable environment on Mars and includes suggested specific measurements for this purpose.

The concept of testing all instruments with analog materials and in simulated and natural Martian analog environments is presented with the selection, collection, and initial characterization of analog materials. Results from the testing of two Relative Humidity (RH) and two RTD temperature sensors are also presented.

The final section provides an outline of the proposed dissertation and the work necessary to complete each of the chapters.

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Table of Contents

Acknowledgements ...... 1 1. Introduction ...... 3 2. Development of Hypothesis and Questions to Answer on the Habitability of Mars ...... 5 2.1. An historical perspective on the exploration and search for prior to the modern space age ...... 5 2.2. “Life”: The continuing saga of a 2500 year old debate...... 8 2.3. Defining Habitable ...... 9 2.4. Habitability of Mars: Background, Measurements and Questions ...... 14 2.4.1. The Exploration and Search for Life on Mars in the Modern Space Age ...... 14 2.4.2. Principle Characteristics of the Mars ...... 14 2.4.3. Water and Energy: Central Strategies to Finding Habitable Environments ...... 16 2.4.3.1. Follow the Water ...... 17 2.4.3.2. Follow the Energy ...... 17 2.4.4. Raw Materials ...... 19 2.4.5. Looking for Life Directly...... 20 2.4.6. Habitability of Mars: Measurements ...... 20 2.4.7. Questions to Quantify the Habitability of Sub-Surface Mars ...... 21 3. Terrestrial Materials and Simulated and Natural Environments as Analogs for Mars Research ...... 22 3.1. What are Analogs, how are they qualified, and how can they be used? ...... 22 3.2. Materials ...... 23 3.3. Simulated Environments ...... 24 3.4. Natural Environments ...... 25 4. Analog Materials Selection, Collection, and Characterization ...... 26 4.1. Analog Material Selection ...... 26 4.2. Field Expeditions for Collection of Analog Materials ...... 28 4.2.1. Mojave Desert ...... 28 4.2.2. Panoche Hills ...... 28 4.2.3. Atacama Desert, Chile ...... 29 4.2.4. Atlas Mountains, Eastern Morocco...... 30 4.2.4.1. Travertines ...... 31 4.2.4.2. Carbonates ...... 31 4.2.4.3. Stromatolite ...... 31 4.2.4.4. Basalt ...... 32 4.2.5. Rio Tinto, Spain ...... 32

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4.3. Analog Material Characterization ...... 33 4.3.1. Methods...... 33 4.3.1.1. Preparation of Samples ...... 33 4.3.1.2. IR Diffuse Reflectance Characterization ...... 34 4.3.2. Results and Discussion ...... 35 5. Sensor Development Testing ...... 37 5.1. Parameters and Ranges...... 37 5.2. Temperature Testing ...... 38 5.3. Relative Humidity Testing ...... 38 5.4. Calibration of RH Sensors...... 41 6. Forward Work Plan ...... 43 References: ...... 47 Appendix A: Table of Material Analogs ...... 56 Appendix B: List of Other Analogs in Figures 4-1 & 4-2 ...... 57

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Acknowledgements

The development of any project relies on the help of many people. I gratefully would like to thank the following people for their generous time, comments, and support. Dr. Gian Gabriele Ori for organizing the Field Expeditions to Morocco and the Rio Tinto and the many great field researchers on these trips who helped in the identification and selection of the analog materials collected for this project. Dr. Julio Valdivia and Saul Perez-Montano who have been steadfast collaborators and friends over the past several years in Peru whose contributions to this project are too numerous to list. Dr. Charles Cockell whose insights into field work are central to the success of this project. Dr. Owen Green of the Earth Sciences Department for help and access to the equipment necessary for processing analog materials. Ian Thomas for help in the initial spectral analysis. As always, Dr. Christopher McKay for his support both financially (under the NASA ASTEP Program) and in the development of the scientific background. And Dr. Neil Bowles for his constant availability and willingness to help “An American Yankee in King Arthurs Court.”

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1. Introduction

Mankind‟s fascination with the search for life beyond the Earth, and in particular on Mars, is the central motivation for this project. The modern space age has had 20 successful missions to Mars which are well documented in many freely available on-line materials; however, a summary of the most important results and their importance to this project is necessary. These are all most directly related to finding water (in either the past or in current conditions) which is considered the key to life (McKay 1998).

Even though Earth based telescopic observations of Mars noted „Canali‟ on the surface (Davenhall 2010), it was Mariner 9 in 1972 which took the first photographs of topological evidence of past water flowing across the surface of Mars (NASA/JPL). Even though there was no evidence of liquid water on the surface at the time of the images, its fate as the principle destination for the search for life was sealed.

A principle goal of the and 2 as the first truly successful landers on the Martian surface was to search for life directly. They had two important scientific experiments: 1) Determination of respiration of soil microbes by adding water to a surface soil sample and measuring the CO2 off-gassing, and 2) Determination of the presence of organic compounds in the surface soil. The results were inconclusive because, while there was CO2 off-gassing in the first experiment, the second experiment resulted in no detection of organics (Anderson, Biemann et al. 1972). A recent result repeating the experiment with a soil sample from the hyper-arid Atacama Desert suggested that the negative result could be attributed to a low temperature setting in the pyrolysis ovens on Viking indicating that the previous results should be interpreted as below the detection limits of the method at the time (Navarro- Gonzalez, Navarro et al. 2006).

The Phoenix mission found subsurface water ice exposed during landing and frozen water droplets were found on the landing struts post lading suggesting the formation of water in a micro-climate under the lander structure (Renno, Bos et al. 2009; Smith, Tamppari et al. 2009).

The MER rover Spirit discovered carbonates just below the surface (Morris, Ruff et al. 2010). These are formed under aqueous conditions and suggest the presence of large, open bodies of water for extended periods of time in the past.

Results of this last summer confirmed the presence of liquid water at the surface in mid- latitudes (McEwen, Ojha et al. 2011) which had been previously suggested as the source for fresh run-off gullies (Malin, Edgett et al. 2006; Heldmann, Conley et al. 2010).

The evidence for water in the past and the existence of frozen and liquid water on present day Mars is extensive, yet no life has been found to date. The surface is little more than a barren wasteland as can be seen in the images on the cover of this report. This puzzling result leaves sub-surface environments sheltered from the harsh environment as the best place to continue the search for life on Mars.

The origin of this project is tied to a NASA Astrobiology Science and Technology for Exploration of (ASTEP) grant. This specific Announcement of Opportunity was created for subsurface sampling and stated as one of the goals, “…the program recognizes a

3 Fletcher Year 1 Report Rev: Final particular need for proposals to aid in the maturation of technology, science data collection, and operations capabilities in the following areas: Surface and subsurface sample acquisition, handling, and distribution…” The project that was submitted (and funded) under this AO is titled “IceBite” and has the goal to develop drill bits and coring systems for drilling up to 2 meters below the surface and collecting a small sample that could be fed into the TEGA ovens as designed for the Phoenix mission (McKay, Andersen et al. 2008). Of the technical design requirements, the most important is to be able to create a ~30 mm diameter deep borehole up to 2 meters deep, while using 50-150 watts of power (Zacny 2005).

The current expectation of IceBite is to take samples from the bottom of the hole and deliver them to analytical instruments located in the main body of the rover or lander, and there is no plan for including sub-surface sensors in the drill string, thus information on the subsurface will not be collected. Unfortunately, taking the sample from the bore-hole without any information of the structure and composition of the surrounding materials means that the resulting data will have no associated context. As an example, the discovery of a variety of aqueous altered materials such as sulfates, iron-oxides, phyllosillicates (clays), or carbonates in the subsurface is an important result in of itself, but down-hole sensors which could determine the transitions of minerals, layering and their thickness would yield length of periods of alteration, suggested processes of alteration, and number of cycles. In short, what are missing from IceBite are down-hole sensors. The future ExoMars mission has included a sensor head mounted on the drill for its Multi-Spectral Imager (MA_Miss) that is located on the main body of the rover, but the separation of the detector head from the instrument via a fiber optics cable could limit the spectral range and possibly the signal to noise ratio. An integrated bore-hole instrument would be the preferred solution.

The goal of this project is investigating the habitability of Mars by designing sensors to look down a small diameter (~30 mm) bore-hole. This will provide good science return in three ways, 1) Details of the bore-hole will be revealed, 2) Provides context for the detailed analysis of samples by surface instruments, and 3) Provides the opportunity for real-time strategic decision making for surface instrument teams. Selected sensors will quantify the habitability of sub-surface Mars and will be tested using analogs including materials, simulated environments, and in situ testing in natural environment analogs.

The following chapters provide:  An historical context for the exploration and search for life on Mars prior to the modern space age  Establishes the hypothesis and questions which must be answered by the selected sensors in order to quantify habitability  Examines the range of environments which must be accommodated (Mars and Analogs)  Selection and testing of preliminary sensors  Selection of and characterization of Analogs (materials, simulated environments and analog environments)  Future work to complete the project

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2. Development of Hypothesis and Questions to Answer on the Habitability of Mars

2.1. An historical perspective on the exploration and search for life on Mars prior to the modern space age.

“Life on Mars!!!”

Imagine for a moment that, in June of 2020, you open up your iPod-8 and this is the headline. I would ask you to put this down for a moment and close your eyes and think about what this might mean to you. In your minds‟ eye, you may see a rover gently drilling below the permafrost to find 2.5 million year old, frozen bacteria; or it may be a heavy lander drilling far below the surface to tap into the liquid water table to find a thriving microbial community; or it could even be a surface sample from an ancient hot-springs that yields up the final evidence of a habitable paleo-environment and long-dead fossilized organisms. How and where it was found is unimportant as the proclamation is all that matters: Life on Mars.

But I again ask the question of you: What might this mean to you? If you have been reading Kant, the philosopher in you might say that the organismalists finally won one over the materialists who have been finding so many exo-planets in the last decades. The poet in you might think of the Arab Abdul Alhazred who said: That is not dead which can eternal lie, And with strange aeons even death may die (Lovecraft 1928).

Figure 2-1: The top half of the chart in the Tomb of Senmut (1534 BCE). The Egyptian god Horus (representing Mars) is conspicuously missing from his position in the boat, but this is because the planet Mars is actually in opposition during this event and is not present near Sirius like the others. Image credit: (von Spaeth 2000)

The Theologian you might say that, “…God will not be less than we thought he was, but more” (Crocker 2010), and that most people wouldn‟t be bothered by having to share the

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universe with microbes, anyway (Olson and Tobin 2008). The engineer and scientist in you might say that it was just a matter of time.

“Just a matter of time?!” you say. Well, yes. Long before the space age and, perhaps, even before recorded history, Mars has held a prominent spot in the hearts and minds of humanity. Just behind the fascination with the Sun and the Moon, Mars was first noticed as a bright, sparkly thing that wandered in front of all the other bright, sparkly thingies in the night sky. When it passed behind the Moon, it was understood that it was further away than the Moon, but closer than the others. Later named a planet (derived from the Greek word “planetes” which means “Wanderer” (IAU 2011)), the first human recognition of Mars is suggested to have been recorded as early as 16,500 BCE in prehistoric cave art in Spain and France (Talbott 1988; Whitehouse 2000; Whitehead 2011). As dubious as this early evidence for the acknowledgement of Mars might be, it was definitely described in the earliest Egyptian star charts which were carved into the roof of the Tomb of Senmut (or Seinenmut) who was the vizier and calendar registrar to Queen Hatshepsut. These star charts (Fig 2-1) showed a very rare and specific and predictable planetary alignment event which occurred in the year 1534 BCE (von Spaeth 2000).

The first direct observation of Mars with a telescope was by Galileo Galilei in approximately 1609 who reported the phases and the spherical shape of the planet (Karol and Catling 2009). While Francisco Fortuna made the first known, albeit crude, drawing of Mars in 1636, the first actual exploration of Mars is credited to who, in 1659 using his improved design for a telescope with a 50x magnification, observed the planet and then hand drew some of the major features of the surface of Mars (Fig 2-2) including the dark region of Syrtis Major (Karol and Catling 2009).

Figure 2-2: The hand drawings of Mars by Christiaan Huygens in 1659. The image to the left contains the “Hourglass Sea” representing Syrtis Major. Image credit: http://planetolgia.elte.hu/icpd/ipcd.html?cim=huygensmars

This led to an explosion in the fascination with the Red Planet, as well as in the explosion in the number of wild and outlandish conjectures of what it might be.

However, the understanding that Mars is another planet is far from the jump to “Life on Mars.” Yet, the idea that these Sky Wanderers might be habitable and full of life is practically as old as the concept of a planetary body. The idea that life might be seeded throughout the , or „Cosmic Pluralism,‟ is generally attributed to the Greek philosopher and astronomer, Thales (c. 624 BCE – c. 546 BCE) (Brake 2006). Unfortunately, the Cosmic

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Pluralism ideology did not last long as (384 BCE – 322 BCE) established the geocentric model of the universe with the Earth at the center and, because of its placement, concluded that the Earth (and life on Earth) must be unique (Brake 2006). This geocentric model, as described by Ptolemy‟s (c. 100 AD – c 170 AD) book, Almagest, was later adopted by the Catholic Church. This effectively ended all debate until (1473 AD – 1543 AD) reestablished the Heliocentric model and reopened the debate on the existence of (Brake 2006). The Catholic Church; however, did not give up without a fight. Giodano Bruno (1548 AD – 1600 AD), an Italian scientist who taught at Oxford, was condemned and burned at the stake by the Inquisition for daring to suggest that, “there might be worlds inhabited with rational beings possibly superior to ourselves.” (Karol and Catling 2009). Cosmotheoros, written by Christiaan Huygens (1629-1695 AD) and published posthumously in 1698, is one of the earliest works on the subject of life of Mars in which he discusses what is required for a planet to be capable of supporting life, speculates about intelligent extraterrestrials, and suggests for the first time that, even though Mars will be colder than Earth, life there will have adapted (Karol and Catling 2009).

Probably the most scandalous accounts of documenting actual life on Mars is attributed to Percival Lowell (1855-1916) who built the Lowell observatory in Flagstaff, Arizona, specifically to search for life on Mars due to his firm belief in the Martian Canals which were “documented” by the Italian astronomer Giovanni Schiaparelli in 1877 (Davenhall 2010). Lowell even went so far as to report the change of colors next to the “Canali” as bands of vegetation because the had to construct these “massive irrigation projects” on the desert planet in order to survive.

These conjectures finally slowed (but have never really stopped!) with the first images of Mars transmitted from the Mariner 4 spacecraft flyby on November 28, 1964, as part of the modern Space Age (Lodders and Fegley 1998). While the understanding of the extreme nature of Mars has improved with the more than 20 successful missions to the planet since, we have yet to discover life on Mars, and are still left with some of the most fundamental questions that keep many a philosopher, poet, theologian, engineer, and scientist up late at night: “Where did we come from?”, “Are we alone in the universe?”, and “What is our future beyond the Earth?” (Morrison 2001).

The search for life on Mars in 2020 begins here and now with the understanding that the conditions on Mars are at the extreme limits of what life can adapt to on the surface, such that life will most likely be found in niche environments that provide the minimum requirements necessary to eke out a meager existence. An understanding of these requirements and the methods and technologies required to establish the habitability of any niche environment, is the first step in the search for life on Mars, and which will guide the evolution of this project.

Thus, the guiding hypothesis for this project is: The subsurface environment of Mars provides habitable conditions sufficient to support life. While the remainder of this project is dedicated to the development and testing of technologies (both in the laboratory under simulated Mars conditions and in Terrestrial based Martian Analog sites) which could ultimately be sent on a drilling mission to Mars, two basic concepts must be defined and understood prior to selection of any hardware. These are what is meant by „Life,‟ and what is meant by „Habitable Environment.‟

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2.2. “Life”: The continuing saga of a 2500 year old debate

The Hypothesis seems clear enough: The subsurface environment of Mars provides habitable conditions sufficient to support life. However, what is meant by the words “life” and “habitable” are central to the development of sensors that could be used to characterize them. Thus, these terms must be examined with a little more depth.

The search for life makes fundamental assumptions on the principle characteristics of life itself. “We will know it when we see it,” (Fig 2-3) as a principle strategy is unlikely to win many grants, but neither can we plan for forms of biology (Fig 2-4) or even Figure 2-3: Calvin and Hobbs non-biological life forms discover an Alien life form when (Fig 2-5) that are radically they see it. different from our basic understanding.

This argument has been raging for nearly 2,500 years as Aristotle is one of the first to define “life” in terms of characteristic life-functions in his book, De Anima, when he Figure 2-4: Alien life in the upper wrote, “Some natural bodies are alive and some are not – atmosphere of giant gas planets by ‘life’ I mean self- may not be based on the basic nourishment, growth, and biochemistry of Earth life. Copyright: Cosmos Magazine, decay” (Matthews cited 2010. Alex Ries. by Kolb (2007)). However, this definition is not sufficiently specific for the search for life on other planets, and many people in the more recent decades have attempted to refine the definition of life (Kolb 2007) as it is central to the design of life-detection experiments (Cleland and Chyba 2002). Figure 2-5: Instead of “...seeking Erwin Schrodinger (1945) discussed the topic of life and out new life...”, Capt. Kirk and said, “It feeds on negative entropy.” Or, simply, that life Commander Spock phaser a new consumes energy to create order. At first glance, this would form of silicon based life that nd doesn‟t register on their appear to violate the 2 law of thermodynamics (…the Tricorder. Copyright: Paramount entropy of an isolated system not in equilibrium will tend to Pictures, 1967. increase over time…); however, this isn‟t the case as the Earth is not an isolated system and has continuous input of solar energy and fresh materials from comets, meteorites, and dust which provide energy and materials needed for growth and reproduction. In the long term, as our Sun slowly dies; however, the 2nd law will be satisfied.

Darwinian evolution based definitions are also quite popular and include NASA‟s working definition of “life” as, “Life is a self-sustained chemical system capable of undergoing Darwinian evolution” ((Joyce 1994; 1994) cited by Cleland and Chyba (2002)). The many thermodynamic and metabolic definitions of life can be summarized by the following

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definition as stated by Davies and Lineweaver (2005) which attempts to combine the concepts of Schrodinger and in, “Life is a carbon-based, complex, organized system that replicates information, maintains a far-from-thermodynamic-equilibrium state by exploiting some form of chemical metabolism, and is capable of evolving by variation and selection.”

The biggest criticism of these, and most other definitions, is that these suffer from both false positives and negatives that satisfy the definition (Ruiz-Mirazo, Pereto et al. 2002). Fire consumes energy and grows and crystals consume energy and produce order, yet neither are alive (Cleland and Chyba 2002; Tsokolov 2009). Small children and mules do not replicate (preventing evolution), yet are clearly alive (Cleland and Chyba 2002). Life is difficult to define because it is as much process as it is substance (McKay 2006). Water was equally difficult to describe in early history before the advent of elemental chemistry when it was finally defined specifically as H2O. Before this it was described as wet, viscous, could be heated and cooled, and could dissolve substances. Simply put, it was described by its properties rather than what it really is (Cleland and Chyba 2002). Life is a much more complicated substance with many complex molecules which vary within our only known example of life, here on Earth, such that life forming on other planets could be even more difficult to define, let alone recognize. For now, the best that we can do is to assume certain characteristics of life that are formulated around terrestrial biochemistry and the conditions necessary to support it.

Carl Sagan (1970) formulated a list of these characteristics which he believed were fundamental to life and which he divided into a variety of categories including physiological, metabolic, biochemical, genetic, and thermodynamic definitions; many other researchers have tried to do the same (Cleland and Chyba 2002). We can reduce these to a simplified set of “requirements for life” (in the broadest sense), in lieu of a definition of life, which then allows us to think about conditions on any planetary body that would satisfy these requirements. For the purposes of this project, the requirements for life are 1) energy, 2) a liquid solvent, and 3) raw materials, all under conditions sufficient to support life. (McKay 1998; Des Marais and Walter 1999; McKay 2006). What that life is and what are the necessary conditions form the fundamental basis for the definition of habitability.

2.3. Defining Habitable

In the discussion of the potential for life on other planets, the word “Habitability” has become common place in the literature, but for the most part is referenced without a precise definition (Shock and Holland 2007). This may be because the habitability of any object is controlled by many competing factors from the physical location of the body itself (Huang 1959; Hart 1979; Gaidos, Deschenes et al. 2005; Tinetti, Meadows et al. 2005; Lammer, Selsis et al. 2010), its composition (Gaidos, Deschenes et al. 2005; Hoehler 2007; Conrad, Fogel et al. 2008; Méndez 2008), the consideration of changes over time (paleo vs. present) (Stoker 2008; Hoehler and Westall 2010), and assumptions regarding the type of biological organisms expected to be found in that environment (Hoehler 2007; Shock and Holland 2007; Hoehler and Westall 2010). More often than not; however, the various authors try to explain why their research refines the understanding of “habitable environments” without ever actually stating which portion of habitability they are researching. The concept of habitability is important to address because it provides a way to constrain the possible distribtuion of life

9 Fletcher Year 1 Report Rev: Final in any system (Hoehler 2007). To avoid the confusion associated with a poorly constrained concept, it is necessary to establish a definition of habitability that is precise enough to have verifiable ranges of parameters.

Rather than try to define what life is, certain requirements of life that are formulated around terrestrial biochemistry and the conditions necessary to support it can be assumed. These requirements include a source of energy, availability of raw materials, and a liquid solvent, all under environmental conditions sufficient to support life. The intersection of Figure 2-6: Classical view of the four requirements for life these, shown in Figure 2-6, intersecting to create a zone capable of supporting life, defined as “Habitable” (Modified from Hoehler (2007)). proscribes a “Habitable” environment (noted as „H‟). It is assumed for now that biological organisms on Mars will be subjected to terrestrial biochemical constraints so that the intersection of conditions and resources will be inhabited by organisms appropriate for that particular subset. Therefore, habitable will be defined as an environment that provides energy, a liquid solvent, and raw materials under conditions sufficient to support life (Hoehler, Amend et al. 2007; Stoker 2008; Hoehler and Westall 2010).

While the reduction to these four items significantly helps to reduce the matrix of potential environmental conditions in the search for life, there are still a large variety and range of specific parameters that influence the ultimate habitability of any planetary body, because habitability is more than just the sum of its parts (Tinetti, Meadows et al. 2005). Flow-Chart 2-1 helps to guide the discussion in the following paragraphs. It starts with the general understanding of habitability that can then be quickly focused to the understanding of habitable environments on Mars. The resulting modifications to the definition of habitability in the context of Mars leads to the selection of parameters (and specific ranges) to measure and which will form the scientific requirements for the development of hardware in this project.

Habitability has been previously been defined in the simplest and most general terms; however, the variety of conditions that allow these terms to be satisfied is considerably more complex. Table 2-1 is a matrix of the parameters which affect and is divided into 6 major topics and which are generalized as follows: 1) Planetary Habitability Zone is the zone in which a planetary body resides from its main sequence star which maintains liquid water at the surface (this is most directly related to the solar constant) (Figure 2-7); 2) Other Solar System to Plantary Dynamics which affect the state of the body (these can be thought of as external forces not including the solar constant); 3) Plantary Dynamics includes all aspects realated to that body (these can be thought of as internal forces); 4) Niche Environments are specialized locations on a body that provide access to

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additional resources or protection from other internal and external forces which would otherwise make a body uninhabitable; 5) The Microbiology Limits address the requirements for life and the range of environmental characteristics which would support those requirements; and, 6) Eco-system Bioenergetics considers specific types of terrestrial organisms and their requirements to survive and grow in extreme environments with limited resources.

Flow Chart 2-1: Flow-Chart Guiding the Definition and Selection of Characteristics to Measure in Order to Assess the Habitability of Sub-Surface Mars

Hypothesis: Mars Subsurface is Habitable (Past & Present)

Parameters Affecting Habitability: this Definition General Definition (Table 1)

Planetary Other Planetary Niche Ecosystem Habitable Solar/Plan. Dynamics Environ- Bio- Micro- Zone System ments Energetics biology Dynamics

Conditions on Mars Modified Definition for Enabling Habitability Mars

Characteristics of Sub- Modified Definition of Surface Mars Enabling Habitability for Habitability Subsurface Mars

Flow Chart 1: Following this flow allows a comprehensive assessment of all characteristics which Which Ones We Are define the potential habitability of any planetary body. Measuring

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Table 2-1: Matrix of Parameters which Affect Planetary Habitability Planetary Habitability Zone Other Solar/Planetary Dynamics  Star Type/Solar Intensity  Gas Giants in outer system to sweep clear large  Distance of Planet from Star class meteorites, asteroids, etc.  Solar Constant Stability of 10^9 years  Stable orbit of body around star or in binary system  Temperatures to maintain liquid water or around giant class planet Strength of Solar Wind  Availability/accumulation of organic material and water ice from comets  Atmospheric Sputtering Planetary Dynamics Niche Environments  Size and Mass  Hot-spring, Hydrothermal systems  Type of core, Geothermal/Volcanic Activity, Plate  Permafrost, subsurface ice, glaciers, saline ices Tectonics  Cryo-ices (highly saline) which stay liquid at very  Type and thickness of atmosphere, Atmospheric- low temperatures (down to ~ -79°C), super cooled surface exchange, Aeolian transport thin water layers down to 180K  Magnetic field  Subsurface aquifers, warm and liquid water, saline  Its own satellite, Internal tidal forces aquifers  Obliquity and planetary rotation rates  Salts (Halite, gypsum) and other hydrated minerals  Standing bodies of water for long periods  Caves, lava-tubes, and eskers  Radiogenic heating  Under rocks including quartz and other crustal  Availability of Organic materials in the surface varieties environments  Surface and shallow sub-surface soils  Geochemistry  Deep sub-surface  Periodic liquid water Microbiology Limits Eco-system Bioenergetics  Liquid Solvent (water), water activity (aw, should  Photosynthetic be > 0.6)  Chemoautotrophic/Chemolithotrophic  Liquid Solvent (ammonia, methane, alcohols,  Methanogenesis other)  Gibbs free energy must support viable reaction  Energy Source (light or chemical)  Limited number of available/Viable substrates -  Terrestrial type biochemistry and Carbon based Biogeochemistry microbiology  Metabolic limits due to high temperatures which dissolve critical organic compounds (> 113°C) and low temperatures which prevent division and growth (< -15°C)  pH  Availability of elements C, H, N, O, P, S

Each of these topics has multiple sub-topics which have been presented and evaluated in the literature; however, there are papers that give a reasonable over-view of each of the major topics and the reader is recommended to review these for more detailed information. Gaidos et al. (2005) and Lammer et al. (2010) review the aspects of the Planetary Habitability Zone, Other Solar/Planetary Dynamics, and Planetary Dynamics; Hoehler (2007), Hoehler & Westhall (2010), and Shock and Holland (2007) review the Microbiology Limits and the Eco- system bioenergetics; and Des Marais and Walter (1999) and the National Research Council (2006) review Niche Environments. Of the 150+ papers and abstracts reviewed to develop Table 1, the phenomena identified in the literature are reduced to the characteristics under each major topic; however, due to limits on space, cross-referencing of the literature to the sub-topic will be provided upon request.

The first consideration in the search for life is looking for a liquid solvent, principally water. The Greek philosopher Thales was once again first when he noted that water constituted the

12 Fletcher Year 1 Report Rev: Final principle of all things (Mansfeld 1985). While he was incorrect that water was the basis of everything (including dirt, rocks, etc.), he was one of the earliest to theorize that there are base materials that form and control the world around us. Water was increasingly identified as not just a necessity, but nearly a requirement. Huygens in his book, Cosmotheoros, defined that life elsewhere must be similar to that on Earth and that water was essential for the existence of life (Huygens 1698). Additionally, he astutely noted that, because pure water would instantly freeze on Jupiter and vaporize on , the properties of water should vary from planet to planet. In more recent decades, the requirement for liquid water was extended to include liquid ammonium, methane, alcohols and other even more exotic substances provided that they are liquid in their local environment.

Figure 2-7: The Planetary Habitable Zone for our Solar System and Beyond.

Image: http://www.wired.com/images_blogs/wiredscience/2010/09/HZ.jpg

This was certainly the start of what would later be identified by Su-Shu Huang (1959) as the Planetary Habitability Zone (PHZ) (Figure 2-7), or the volume around a sun (defined by minimum and maximum distance from a specific solar energy intensity) in which a main sequence star would provide stable luminosities (and temperatures) over at least 109 years necessary to support the development of life. This was extended by Michael Hart (1979) to connect the PHZ more specifically to the distances from a sun which maintain liquid water on the surface of a planetary body. In more recent years, the idea of “niche” environments providing liquid water (and other liquid solvents) beyond the traditional “Planetary Habitable Zone” has allowed the inclusion of locations like , , Enceledus, and Io as potentially habitable bodies, making the traditional definition of the PHZ nearly obsolete (at least in terms of our Solar System), though the PHZ definition is still quite useful in the search for habitable exo-planets beyond our Solar System.

A final consideration for our strategy is that many environments are unlikely to be completely classifiable as “Habitable” or “Not Habitable.” This is especially true when we consider an

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environment through major time periods as the conditions in that environment may vary considerably over time allowing a “part-time” or “partially habitable” environment.

2.4. Habitability of Mars: Background, Measurements and Questions

2.4.1. The Exploration and Search for Life on Mars in the Modern Space Age

Mars has been under direct study since the early stages of the Space Age with 20 (successful) missions arriving to examine and explore the Red Planet. There are ongoing missions: (Mars Express (2003), Mars Exploration Rover – “Opportunity” (MER-B, 2003), and Mars Reconnaissance Orbiter (2005); there are upcoming missions that are departing this year: Mars Science Laboratory; there are missions in the planning stages for launch in 2016 and 2018: ExoMars: plus there are others conceived of for the next decade (Taylor 2010; JPL 2011). A wealth of data has been analyzed and our understanding of the development of Mars from its early days (~4 Gyr) to the present day is ever increasing. However, what we know is only a few millimeters deep (in the case of satellite remote sensing missions) to a few centimeters (in the case of Viking 1 & 2, Pathfinder, Spirit and Opportunity, and Phoenix). We know that the surface of Mars is nearly incapable of supporting life, such that sub-surface environments are some of the best places to look. This begs the question of what should compact, subsurface sensors look for? The answer to this starts with a review of what we already know about Mars.

2.4.2. Principle Characteristics of the Planet Mars Table 2-2: Characteristics of Mars

While there is much yet to learn about Characteristic Value the history and evolution of Mars, the Orbit semimajor axis 1.52366 AU current atmospheric and surface Orbital Period 686.98 Earth Days Mean Solar Day 24 h, 39.6 m conditions have been fairly well Mass 6.4x10^23 kg characterized. A list of important Mean Radius 3389.92 km parameters which most affect Solar Constant at Mean Distance 588.98 W m^-2 planetary habitability are provided in Obliquity 25.19° Table 2-2, for completeness; however, Mean Atmospheric Pressure @ Surface 5.6 mbar Principle Atmospheric Composition CO2 ( 95%) the reader is referred to the many available (including free online) resources for more detailed information.

It is believed that the environment on Mars at 3.8 GYR was nearly the same as the Earth at that time with a thick CO2 atmosphere, highly active volcanism, Figure 2-8: a liquid core, a magnetic field, an obliquity similar to Mariner 9 Image Earth, and large open bodies of water (possibly seas in PIA02094. the northern hemisphere and freely flowing water NASA/JPL throughout the rest). The principle differences to Earth A are the much smaller size (and associated gravitational field), no tectonic plates, no large moon, and an apparent lack of radiogenic heating. The early conditions made Mars warm and wet while current conditions leave it cold and dry. The reasons for this

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Fletcher Year 1 Report Rev: Final shift from a Warm, Wet Mars to the current Cold, Dry Mars is not well understood, and conjecture is beyond the scope of this report. The topology and morphology of the surface support the theory of a Warm, Wet Mars and open bodies of water (Figure 2-8). Much of the

2-9 A

Figure 2-9; A: At -30°, Surface temps can reach nearly 300K at the start of the southern summer. B: Example of sub-surface temps which stabilize at ~-50°C at only 15cm below the surface (Carr 1996). aqueous altered materials found on the surface today such as hematite, sulphates, phyllosillicates, and carbonates are believed to have formed during a warm, wet Mars as all of these would have required significant periods of time exposed to water.

With no visible life-forms found to date, present day Mars would seem to be a lifeless planet. While the majority of the time the surface temperatures are below the temperatures required for biogenic 2-9 B activity, temperatures can rise to nearly 300K (Figure 2-9 A) which is more than sufficient to support liquid water on the surface under current conditions. Subsurface temperatures are more stable and an example of calculated sub-surface temperatures at 22° latitude (Figure 2-9 B) indicates that saline saturated solutions (cryo-brines) could easily be

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Fletcher Year 1 Report Rev: Final liquid under current conditions (Möhlmann 2009) and recent results from Mars obeservations have shown this to be the likely cause of liquid water at the surface (McEwen, Ojha et al. 2011).

Micro-climates are another important consideration as even under current conditions liquid water was produced on the landing struts of the Pheonix Lander while it was sitting on top of newly exposed, sub-surface ice. Water-ice should sublime directly to vapor after exposure to the current atmospheric conditions; however, salts on the struts deposited during the landing sequence, combined with the right orientation of the sun and a possible pocket of increased pressure under the lander from trapped water vapor, presumably caused a micro-climate which allowed liquid water droplets to form. Figure 2-10: Mars at High (25°) and Low (45°) Obliquity. The idea of partially habitable conditions was previously introduced (Section 2.3). An important characteristic of Mars is the fact that its axis of rotation (Figure 2-10) precesses over millions of years (Figure 2-11) with the duration of low obliquity lasting about 5 million years (Laskar, Levrard et al. 2002). The low obliquity angle provides about 2 times as much solar incident radiation at the surface during the summer as compared to the high obliquity angle. This provides enough additonal heating to allow liquid water on the surface of the northern hermisphere for a significant period of time. Subsurface temperatures would also be correspondingly higher.

In terms of this project, the most important characteristics throughout the history of Mars are Figure 2-11: Calculated period of Mars precession angle over time. (Source: Laskar et al., 2003). those that are related to forming habitable environments (most importantly, liquid water) which could have lead to the genesis of life, or at least the support of life seeded through the deposition of meteorites on the surface, and/or provide for habitable niche environments under the current conditions. The path to qualification of habitable environments starts with two key strategies.

2.4.3. Water and Energy: Central Strategies to Finding Habitable Environments

Finding habitable conditions on any planetary body is not simple because the parameters that control them are not separate and independent. The complex interactions between all of the parameters (Table 2-1) can make the search for a habitable environment quite daunting. A detailed analysis of these parameters in relation to Mars is the thing that books are made of and well beyond the scope of this report (and probably the full dissertation); however, in terms of the search for habitable environments on Mars, two important strategies can be selected which significantly reduce the number of parameters to measure, and can serve as a

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Fletcher Year 1 Report Rev: Final first order approximation of the best place to look. These are “Follow the Water” and “Follow the Energy.”

2.4.3.1. Follow the Water

NASA adopted the mantra of “Follow the Water” as the central strategy guiding the selection, design and development of the majority of their Mars exploration programs (McKay 1998), as does this project. The parameters which most control the various forms of water (liquid, brine, frozen, or vapor) are the position of Mars in the Planetary Habitability Zone, the evidence of long standing bodies of water, its geochemistry and hydro-geothermal activity, subsurface environments which have ice, permafrost, liquid water, salts which trap water and change the salinity, and its obliquity.

The distance from the sun most directly affects presence of liquid water on the surface. At a first glance of the Figure of the Planetary Habitability Zone, it would appear that Mars is just outside of the traditional calculation for the Planetary Habitable Zone; however, there is significant evidence for liquid water on the Martian surface at the same time as the emergence of life on Earth (3.8 to 4 GYR) and under present (McKay 1998; McKay 2006).

There are two principle methods of determining if there was liquid water in the past: Morphological/Topographical evidence and/or the presence of aqueous altered materials (Murchie, Mustard et al. 2009), such as Iron Oxide, Jarosite, Hemitite, phyllosilicates, and Carbonates. The type of materials and the extent of layering of these materials (stratigraphy) will indicate if water was present, for how long, the types of geological processes which formed them, and the geological cycles. Searching for water in order to determine habitability in the present day or in partially habitability periods includes looking for water trapped in rock or permafrost and looking for minerals or salts that are known to trap moisture that could either provide liquid water to an active microbial community in the present or protect microorganisms until conditions are more favorable in the case of partial habitability. The salinity of water/ice/permafrost is also an important consideration as this can shift the freezing point of liquid water to nearly -79°C in the case of Cryo-brines (Möhlmann 2009). Salts, such as perchlorate which could produce a cryo-brine, were discovered by the Phoenix mission (Hecht, Kounaves et al. 2009; Möhlmann 2009) and could be the key to the recent liquid water results reported for Mars (McEwen, Ojha et al. 2011).

2.4.3.2. Follow the Energy

In more recent years, the mantra of “Follow the Water” has been succeeded by many copy-cats of Follow the “whatever-you-are- looking-for.” The only one of these that really makes sense; however, is “Follow the Energy.” The most useful energy sources for biological organisms are solar incident radiation and chemical.

Photosynthetic life forms (those which Figure 2-12: Halite salt formations in the Atacama Desert utilize light or photons as their energy with a line of green hypoliths just below the surface as source), by definition, must have access to indicated by the arrow. (Image Credit: Fletcher 2006).

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Fletcher Year 1 Report Rev: Final solar incident radiation and therefore must be resident on the surface or within special niches which shelter the organism from any extreme environmental conditions while still providing access to light, a liquid solvent and raw materials (Fenchel, King et al. 1998; Rittmann and McCarty 2001; Madigan, Martinko et al. 2010)1.

Chemosynthetic life forms (those which utilize a chemical source of energy), do not need light and; therefore, can reside in even more remote and hidden niches away from the surface of the body (but these still must provide access to a liquid solvent and raw materials). These environments represent some of the most promising opportunities for the discovery of life on other planetary bodies within our Solar System beyond the PHZ, so a basic understanding of how biological organisms generate energy from chemical reactions is necessary in order to reduce the rather large number of potential reactions into a manageable subset of the most likely available on Mars.

The Gibbs Free Energy (ΔG0‟) of a chemical reaction, or the amount of energy available to a biological organism for synthesis from the oxidation-reduction of a substrate and a product, provides a quick assessment of the potential habitability based upon the types of materials present in a specific environment. In this calculation, the free energy of formation of an element or compound for the reactants of a chemical reaction are subtracted from the free energy of formation of the products. The net result must be a negative value, or exothermic, in order for there to be energy available for synthesis. Reactants can be organic or inorganic substances and can be from naturally formed compounds in rocks, incident comets and meteorites, or formed by biotic processes. Evaluations of the types of reactants available in an environment, along with an estimation of the potential types of products, can give a first order approximation of a habitable environment (from an energy perspective). Certainly, the explanation of this is much more complicated than space allows in this report; however, this is a very powerful assessment as the calculation of a negative Gibbs Free Energy is independent of consideration of any specific type of organism. A more detailed analysis of how to “Follow the Energy” can be provided in the Year 2 Report.

Much like “Follow the Water,” “Follow the Energy” also considerably helps to narrow the scope of where to look for life.

In the case of photosynthetic organisms and light, the only types of life that are reasonably possible on Mars are cyanobacteria in the forms of endoliths living in salt formations (Wierzchos, Ascaso et al. 2006) like those found in the Atacama Desert (Figure 2-12); chasmoendoliths living in the cracks of semi- transparent quartz stones (Warren-Rhodes, Rhodes et al. 2007); and hypoliths (Figure 2-13) living under semi-transparent quartz stones (Warren-Rhodes, Rhodes et al. 2006). These are interesting for two reasons. First, the salt and stone provide a protective environment that still allows light to pass through to Figure 2-13: Upturned Quartz the microorganisms living inside or under the quartz/salt, and rock from the Atacama Desert second, both the salt and the quartz serve as a water trap to shows thin layer of Hypoliths collect moisture from the humidity in the air. Salts in the form of (Warren-Rhodes et al, 2006) Gypsum (Calvin, Roach et al. 2009; McDowell and Hamilton

1 The information in this section, including the following paragraphs, was compiled from these three sources.

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2009) and Halite (Osterloo, Anderson et al. 2010) as well as quartz (Osterloo, Anderson et al. 2010) have all been discovered on Mars and could serve to support these organisms under the current conditions.

In the case of chemosynthetic organisms, the bioenergetics will dictate if a substrate will provide a viable source of energy from a reduction-oxidation reaction. Principle species which could exist in Mars sub-surface environments and provide energy to organisms for + - metabolism and growth include (as a preliminary first analysis): H , HO , H2O2, O2, C - (graphite), H2CO3, HCO3 , Alcohols (Methanol, Ethanol, etc.), Monocarboxylic acids (Formate, Acetate, Propionate, Pyruvate, etc.), Dicarboxylic-acids (Oxalate, Succinic acid, Succinate, Fumaric Acid, Fumarate, etc.), Amino Acids, Purines, Aromatic compounds, NH3, + - - - - 2- - - 2+ 3+ HN4 , NO2 , NO3 , N2H4, ClO2 , ClO3 , S , SH , SH2, HSO3 , Fe , and Fe (Table 15, Gibbs free energies of formation from the elements for compounds of biological interest, (Thauer, Jungermann et al. 1977). While none of the organic compounds listed above have been found to date on Mars (either of biotic or abiotic origin), many have been found in comets which do make it to the surface of Mars and which could serve as an energy source for microorganisms. The identification of any of these in a subsurface environment that has already been shown to have (or had) access to a source of water, would be an important step in the qualification of the habitability of that location for past, present and partial habitability.

2.4.4. Raw Materials

The final step in the qualification of the habitability of a location will be the identification of a specific set of elements required for the building of cellular material. These vary between species as is noted in Table 2.1 (Empirical chemical formulas for prokaryotic cells) of Rittmann and McCarty (2001), but the basic empirical formula for a cell is C5H7O2N which can be used for the balancing of the bioenergetics. It should be strongly noted that this chemical formula only represents the elements and their concentrations in a typical bacteria and does not in any way indicate the overall structure; however, this does allow us to identify important base elements required for the metabolism and cellular growth that must be present in the environment. It is worth re-iterating that this is based on terrestrial microbiology and biochemistry and that true Martian organisms may have a distinctly different cellular structure, use of elements, and/or biochemistry. Nevertheless, the elements C, H, O, N, S, and P have been noted as the full list of elements which should be present in the target environment as necessary for metabolism and growth (McKay 2006; Hoehler, Amend et al. 2007; Hoehler and Westall 2010; Shkrob, Chemerisov et al. 2010; Stoker, Zent et al. 2010).

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2.4.5. Looking for Life Directly

While the purpose of this project is principally to quantify the habitability of the subsurface of Mars, it is always a possibility that direct signs of life may be present at the time of the measurement. In this case, it is important to be prepared with the understanding of the response of the system due to the presense of fossilized life forms (past) or even microbes frozen into the permafrost and ice (present). A good example of a fossilized terrestrial life form are the stromatolites (Figure 2-14) which are some of the earliest forms of life which will alter their surroundings and provide a Figure 2-14: 600 Myr old Stromatolite from good example of something that might be Morroco. Image Credit: Fletcher 2011. detected by its spectral signature.

Because of the cyclical nature of the obliquity of Mars, there are periods of many millions of years with tempetures warm enough for liquid water at the surface. Based on evidend3e from the evolution of early life on Earth, this would be plenty of time for the establishment of large communities of water based, microorganisms. During the rest of time, as is the case for present day Mars is, surface temperatures are below the freezing point as well as the metabolic rates of the most cold resistent terrestrial microorganisms (Amato, Doyle et al. 2010). While this would leave any resident microorganisms frozen for several millions of years at a time, this is not considered to be an impossible boundry to overcome as dormant organisms have been recovered from >5Myr old ice (Gilichinsky, Wilson et al. 2007) and are theorized to be able to survive for as long as 250 million years (Marion, Fritsen et al. 2003). Because of this, it would be very useful to be able to measure a spectral signature of microorganisms trapped in a sub-surface, icy environment (McKay 1998; McKay 2006). As part of the testing in this project, water will be seeded with photosyntetic organisms and frozen down and then tested to determine at what concentrations these organisms could be detected by the sensors.

2.4.6. Habitability of Mars: Measurements

In terms of identifying the presence water, it is possible that the presence of water in the subsurface environment could be determined through the determination of Relative Humidity (RH) in the bore-hole atmosphere. Drilling missions in the next decade are likely to be limited to no more than about 2 meters of depth. Because of the current environmental conditions on Mars, any source of water withing 2 meters of the surface is most likely to be water trapped in rocks, ice, or permafrost. A recent result which has not been well acknowledged is associated with drilling in simulated Mars conditions (temperature, pressure, atmospheric composition) which was completed as part of doctoral dissertation work by Kris Zacny at the University of Berkeley in 2005 (Zacny 2004; Zacny 2005). In this work, he found that the heating associated with drilling caused the direct vaporization of water frozen into rocks which then expanded to near 170,000x volume because of the pressure differential on Mars. This cleared all debries from the bore-hole, but what has not been previously

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Fletcher Year 1 Report Rev: Final considered is that there will likely be a residually RH left in the bore-hole as compared to typical RH on Mars. The residual heat of the drilling which will continue to vaporize the newly exposed subsurface ice. Additonally, the exposure of the ice in the bore-hole to the atmosphere will cause it to sublime directly to vapor. Both of these mechanisms will raise the RH in the bore-hole and can be used as a proxie for the determination of the presence of water trapped in ice, permafrost, or rocks in sub-surface Mars. Another possiblility may be to add a water spectral channel and try to measure water vapor with the spectrometer/radiometer.

The identification of materials which could provide a chemical source of energy and the raw materials for building can be accomplished with the measurement of the spectral signature from the use of an in situ spectrometer or radiometer.

2.4.7. Questions to Quantify the Habitability of Sub-Surface Mars

In conclusion of this section, a series of specific questions are proposed. The answers to these could be used to quantify the habitability of subsurface environment of Mars in all of its epochs. Table 2-3 provides a listing of these questions, marks its applicability to habitability, and identifies a method of measurement. These are used to guide instrument selection, design, and testing throughout the rest of the project.

Table 2-3: Questions and Instruments for the quantification of Mars Subsurface Habitability

Habitability Instrument Cat. Question Past Present Partial Spectr. Temp/rH I What is the subsurface temperature? X X X I Is there water trapped in the rocks? X X X I Is there permafrost? X X I Can we determine salinity? X X X I Are there aqueous altered materials? X X I What is the stratigraphy? X X X X I Are there salts (gypsum, halite or other)? X X X II Is there a chemical energy source? X X X X III Are there the raw materials? X X X X IV Can we detect organisms? X X X X Category: I – Water; II – Energy; III – Raw Materials; IV – Direct Detection of Life

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3. Terrestrial Materials and Simulated and Natural Environments as Analogs for Mars Research

3.1. What are Analogs, how are they qualified, and how can they be used?

Setting the parameters to measure is the first step, but there must be a way to reliably test them on Earth. The use of Simulants and Analogs is one of the Material most powerful tools available to research scientists and engineers because access to actual materials is limited (as in the case with Lunar materials) nor near non-existent (as in the case of Martian materials) (Seiferlin, Ehrenfreund et al. 2008). Optical Environment Their use has become commonplace throughout the community and will be central to the development and testing of hardware in this project. But the first questions that must be answered are Figure 3-1: Principle Categories of Types of Analogs. what is an analog, how are they qualified, and how can they be used?

One way to organize the division of the variety of analog types is by Material properties, Optical Properties, and Environment (Figure 3-1). Material properties comprise the physical characteristics of the material (e.g., density, particle size, mechanical strength, etc.). Optical properties comprise light reflectance properties of the material. While Optical properties are technically due to the physical characteristics of materials, for the purposes of this project, they will be considered as a separate category. Environmental properties comprise the local conditions that will change the physical or optical properties of a material. They are also central to the classification of the habitability of a specific environment.

These are used to group the properties which define and qualify a material and environment (simulated or natural) as an analog, and under what conditions they may be used and maintain the qualification. There are many characteristics (Table 3-1) and any one material or environment could simulate one or more of these at once. The path to qualification for each item is independent and it is important to establish a set of criteria and procedures that lead to qualification and it is important to note that once qualified, the material and/or environment can only be used for this combination of conditions (for example, a good mechanical analog may be a poor optical analog. The qualification process includes analysis, testing, and simulation. All analogs used in this project will be selected and qualified according to pre- established procedures. While full details of the qualification process are beyond the scope of this report, they will be provided as part of the full project documentation (either within the thesis or as supplemental material as is appropriate).

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Table 3-1: Detailed Listing of Measurable Characteristics of Analogs

Material

Chemical Physical: General Physical: Thermophysical  Dielectric Constant  Particle Size  Albedo  Redox Potential  Particle Shape  Thermal Inertia  pH  Relative Density Magnetic  Electric Conductivity  Total Density  Magnetic Susceptibility  Volatiles  Porosity  Magnetic Saturation  Mineralogy  Water Content Organic Mechanical Physical: Geological  Total Organic Carbon  Cohesive Force  Morphology  Molecular Abundance  Internal Angle of Friction  Geologic Processes Microorganism Content  Depth of Layer Environment Optical  Temperature  Spectral  Atmospheric Composition  Diffuse  Atmospheric Pressure  Bi-Directional  Ultra-Violet Light  IR  Near IR  Mid IR  Visible *Note: Table compiled from Valdivia (2008), Marlow et al. (2008), and Sabille & Schlagheck (2005).

3.2. Materials

The use of analogs for planetary exploration was first suggested by Hubertus Strughold in 1953 in order to test the survivability of terrestrial organisms in simulated Mars conditions (Hagen, Hawrylewicz et al. 1964) and who later ran the first of these simulations which included environmental and analog materials in 1958 (Kooistra, Mitchell et al. 1958).

The first true simulants, complex terrestrial materials which were designed to mimic multiple characteristics of a non- Figure 3-2: Astronaut Buzz Aldrin uses a lunar soil sampling tool which was tested with Lunar Simulants earth material, was in the mid 1960‟s prior to Apollo 11. (NASA 1969) during the Apollo program in which a team led by J.K. Mitchell at UC Berkeley developed 35 Lunar Soil Simulants (LSS) (Mitchell et al. (1971), NASA (1969) and Sibille et al. (2005)). These were used to simulate the lunar surface for evaluation of compaction and settling during landing, walking, and science tasks, plus thermodynamics and emissivity; all necessary for detailed planning of the first Manned Moon Missions.

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The Mars Mariner 9 remote sensing mission was the first time in which the optical properties of analogs materials were used for the interpretation of spectral signatures from an instrument (the Infrared Interferometer Spectrometer (IRIS)) which was in orbit around another planetary body (Hanel, Conrath et al. 1970).

These early results paved the way for the use of analogs; however, what qualifies a simulant or analog material as such is poorly defined and varies significantly. While limited in scope, an accepted definition proposed during the Workshop on the Production and Uses of Simulated Lunar Materials at the Lunar and Planetary Institute (Houston, USA) in 1989 (Mckay and Blacic 1991; Seiferlin, Ehrenfreund et al. 2008) is as follows:

„„Any material manufactured from natural or synthetic terrestrial or meteoritic components for the purpose of simulating one or more physical and/or chemical properties of a (lunar) rock or soil.‟‟

In the Mars missions of the last two decades, analog materials have been used to interpret spectral signatures in order to explain the evolution of the Mars geology and mineralogy (Bishop, Pieters et al. 1993; Bishop, Pieters et al. 1995; Esposito, Colangeli et al. 2000; Bibring and Erard 2001; Bishop, Murchie et al. 2002; Poulet, Bibring et al. 2005; Johnson, Grundy et al. 2006; Johnson, Grundy et al. 2006; Chevrier and Mathe 2007; Morris, Ruff et al. 2010)

3.3. Simulated Environments

Much in the same way as material analogs, simulated environments have been in use since the beginning of the Space Age to simulate the harsh operational environments in the qualification of space flight hardware. This was later extended to include the simulation of planetary processes such as geology and mineralogy (Stoker and Bullock 1997; Chevrier and Mathe 2007; Seiferlin, Ehrenfreund et al. 2008), atmospheric (Kooistra, Mitchell et al. 1958; Hagen, Hawrylewicz et al. 1964; Chevrier and Mathe 2007), and biological (Kooistra, Mitchell et al. 1958; Hagen, Hawrylewicz et al. 1964; Foster, Winans et al. 1978; de Vera, Horneck et al. 2004; Cockell, Schuerger et al. 2005; Marlow, Martins et al. 2008; Olsson-Francis and Cockell 2010). Simulated environments will be used in this project to test methods and hardware at Mars temperatures, humidity, pressures, and atmospheric composition in order to ensure that results match what the instruments would see on Mars. These environments will be combined with

Mars Analog Materials for many of the tests. Figure 3-3: Chamber at AOPP which will be used to Simulate Mars Environmental Conditions.

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3.4. Natural Environments

Testing in natural environments is increasingly becoming a central part of projects relating to the search for life beyond the Earth. Recent years have acknowledged the limitations in the use of analog materials in laboratory settings as their removal from their natural environment quite often change the very nature that resembles another planetary body such as microstructure, humidity, natural temperature, pore space, ambient pressure, and other key parameters (Seiferlin, Ehrenfreund et al. 2008). As can be seen in the cover images, Mars is dry and barren and simulated environments cannot test hypotheses, methods, and technology in the same way as can the natural environment. Interestingly enough, only the bottom of these two images is from the surface of Mars, while the top image is from the hyper-arid, Mars Analog, Atacama Desert. Except for the color changes from Photoshop, the two environments look astonishingly similar, and do indeed have many of the same features: barren, hyper-arid, and devoid of any visible life. For this reason, the use of in situ studies of natural environments is the last and most important step in understanding how data from analogs can be directly compared to remote sensing data sent from Mars.

There are few Natural Analog environments to Cold, Dry Mars (Figure 3-4). As the environment moves from wetter to drier and from warmer to colder, frozen, pure water will convert directly to vapor as indicated by the dashed line in Figure. Mars, at its lowest obliquity of 45°, just crosses under the line (due to low atmospheric pressure). At high obliquity of 25°, only special conditions or increased salinity will allow the formation of liquid water on the surface.

The University Valley is part of the Dry Valleys in Antarctica and is the Figure 3-4: As conditions move from warm to cold and moist one of the only open, landmass to dry, environments cross the line where water ice sublimes directly to vapor. locations on Earth that crosses the liquid/vapor boundary because of the low temperatures. This location combines low temperatures with nearly no rainfall that makes it the best Cold, Dry Analog on the planet. Coastal locations in the Dry Valleys (such as Taylor Valley) have significant moisture input and even open bodies of liquid water in the valley floors in the summer, while University Valley only has sub-surface permafrost. Another key analog to dry conditions is the hyper- arid Atacama Desert that is the driest desert on earth. These two locations are under planning for use as part of this project.

There are many other locations throughout the globe that provide analog materials, and it is important to test in situ whenever possible, even when the environmental conditions do not match Mars conditions.

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4. Analog Materials Selection, Collection, and Characterization

4.1. Analog Material Selection

Material analogs will be used to test and validate the design of sensors to measure the spectral signatures of similar materials to those found on Mars. There is a significant body of work in the literature detailing the detection and identification of a variety of materials on the Martian surface which is beyond the scope of this report. The reader is referred to several papers for additional information (Mustard, Murchie et al. 2008; 2009; Ehlmann, Mustard et al. 2010; Pio Rossi and van Gasselt 2010); however, Table 4-2 provides a detailed summary of these materials, where they have been found on the surface of Mars, their Terrestrial Analog equivalent (with location), and references. Figures 4-1 and 4-2 marking where these are found on Earth and Mars, respectively.

While it would be impractical to work with every material identified on Mars to date, at some risk of over-simplification, a reduced set can be determined from the previously stated strategies: Group 1: those that are necessary for building cellular material; Group 2: those that can be utilized as a chemical energy source; Group 3: those that were formed through an aqueous process (indicating liquid water on the surface of Mars); and Group 4: and those that provide a current niche habitat (such as salts).

Group 1 have already been specified as C, H, N, O, P, and S. It should be noted that these are typically drawn from the minerals themselves, and are not separate and will not be tested in this project independently. It is assumed that the mineral choices from Groups 2 and 4 will provide these necessary elements.

Group 4 are limited here to two specific salts that have been found to provide a niche environment to cyanobacteria (photosynthetic organisms) in the heart of the Hyper-Arid, Mars-Analog, Atacama Desert. These are Halite and Gypsum. Group 2 materials have the requirement to provide a sufficient Gibbs Free Energy of formation from an Oxidation- Reduction paring of materials; however, most of the materials in the others groups can be utilized as an energy source under the right circumstances, such that no specific material will be identified as belonging only to Group 2.

Table 4-1: Categories of Aqueous Altered Materials. Category Representative Minerals Mineral Selected Oxi-Hydroxides Hematite, Goethite Hematite Carbonates Calcite, Sidrite, Magnesite Calcite Fe-Sulfates Jarosite, Halotrisite, Alunite Jarosite Sulfates Barite, Gypsum, Halite Gypsum, Halite Phyllosillicates Al-phyllosilicates, Fe/Mg Montmorillonite, Serpentine Smectites, Montmorillonite, Serpentine SiO2 Quartz Quartz *Note: Table modified from Valdivia (2008).

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Figures 4-1 & 4-2: Comparison of Similar Materials Found on Both Earth and Mars

http://Jmars.asu.edu; Christensen et al. (2009) Figure 4-1 Table 4-1: Location of Similar Materials Found on Both Earth and Mars Sample Sym Location: Earth Location: Mars References Ca-Carbonate (2) Morocco Gusev Crater Morris et al. (2010) Basalt (2) Morocco, Iceland Meridiani Planum Rieder (2004) Gypsum Pomaia, Italy Juventae Chasma, Iani Chaos Gendrin (2005) Limestone Morocco Gusev Crater Morris et al. (2010) Halite Hampton Corners, NY, USA Meridiani Planum Bridges & Grady (1999) Rieder (2004) Jarosite (2) Panoche (USA), Rio Tinto (Spain) Meridiani Planum Golden et al. (2008) Quartz (2) Purchased from Fisher & Acros Generally Abundant Bandfield (2002) JSC Mars-1 Pu‟u Cinder Cone, Hawaii, USA General Spectral Morris et al. (1993) Montmorillonite Panther Creek, MS, USA Syria & Lunae Planum Bishop(1993) Hematite Republic, Michigan, USA Meridiani Planum Christensen et al. (2001) Desert Sand (9) Mojave, California, USA Generally Abundant Allen et al. (1998) Atacama (Chile) Fletcher et al. (Submitted) a&b Future Samples (3) Desert Sands: Peru, Antarctica Generally Abundant Allen et al. (1998) Sulfates: Italy (Naples Solfatara) Ius, Hebes, Capri, Candor Gendrin (2005) Other Analogs Various Various Appendix B Note: represent Samples Already Collected, Diamonds To Be collected, and Circles other potential analogs as necessary Figure 4-2 http://Jmars.asu.edu; Christensen et al. (2009)

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Group 3 is the final group that has many variations of aqueous altered materials. Table 4-1 shows a reduced set of general categories of materials as well as representative minerals which fall under that category, and the specific mineral which has been selected to represent that category for the purposes of this project. These provide an indication of past water on Mars, but also provide the energy source and elements needed for Groups 1 and 2.

A sub-set of materials were selected for use in this project. These are marked in Figure 4-1 with stars, colored according to the key in Table 4-2. Appendix A provides a detailed listing of all samples collected for use as Material Analogs. Of the 22 samples selected, the Hematite, Montmorillonite, Halite, and Gypsum samples were purchased from Wards Natural Sciences Company. While specific location information was not provided by Wards, through very clever on-line sleuthing and use of Google Earth, the GPS coordinates and source were determined for each of these samples. The Quartz samples were purchased from Fisher Scientific and the Acros Chemical Company, and JSC Mars-1 was provided by NASA. All other samples were collected during Field Expeditions. Principle Field Expeditions included the Atacama Desert, Chile, the Eastern Atlas Mountains, Morocco, and the Rio Tinto, Spain. Several other samples were collect from key locations in California and Iceland at moments of opportunity. Also listed on this table is a review of the literature indicating additional material analogs that could be selected to expand the data set during the development of the project.

4.2. Field Expeditions for Collection of Analog Materials

4.2.1. Mojave Desert

Panoche The Mojave Desert is an Death Hills arid desert located in the Fresno Valley south western United States in Southern California. A single sample of desert sand was collected in 2003 Bakersfield for this project from the Little Mars Analog site at the Red Hill Little Red Hill, located http://www.geomapapp.org northwest of Silver Figure 4-3 Lake near Baker, California at 35°23 N and 116°16 W at an elevation of about 514m at the northeastern part of the Mojave Desert (Navarro-Gonzalez, Rainey et al. 2003; Bishop, Schelble et al. 2011).

4.2.2. Panoche Hills

The Panoche Hills is an arid environment with a significant deposit of natural iron sulfate in the form of Jarosite (Strawn, Doner et al. 2002). These types of materials are often formed on top of sedimentary rocks of marine origin in a low pH aqueous environment. The Panoche Hills and Jarosite from this location have been qualified as Mars Analogs in the development, testing, and qualification of the Mars Organic Analyzer (MOA) which is a NASA-ESA

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Figure 4-4: Field Expedition to the Mojave in 2003. Little Red Hill is to the right with the researchers on top.

4.2.3. Atacama Desert, Chile

Hyper-arid environments http://www.geomapapp.org represent some of the most challenging habitats on Earth, Antofagasta often limiting ecosystems in these locations to little more than microbial life (Fletcher, Conley et al. 2011). The Figure 4-5 Yungay Atacama Desert on the western coast of South America is one of the world‟s driest deserts European Southern and exhibits desert conditions Observatory - Paranal extending from 10ºS to 30ºS, crossing from Perú into Chile. The values of mean annual precipitation reported for northern Chile are the lowest of any long-term record in the world (Dillon and Hoffmann-J. 1997), and precipitation averages less than 1 mm/year in the central regions between about 15ºS to 25ºS (McKay, Friedmann et al. 2003; Valdivia-Silva, Navarro- González et al. 2011). The combined effects of a high pressure system located on the western Pacific Ocean, the drying caused by the cold, north-flowing Humboldt Current, and the rain shadow of the Cordillera de Los Andes intercepting precipitation from the Inter-tropical Convergence, causes this hyper-arid climate (Arroyo, Squeo et al. 1988; Houston and Hartley 2003).

This wide spread hyper-aridity does not support macroscopic primary producers (Figure 4-6), nor does it appear to support abundant microbial photosynthetic communities (Warren- Rhodes, Rhodes et al. 2006) beyond specialized niche communities such as endolithic cyanobacteria hidden in halite salt outcroppings (Wierzchos, Ascaso et al. 2006) and sub- surface bacterial communities (Maier, Drees et al. 2004; Drees, Neilson et al. 2006; Fletcher, Conley et al. 2006; Fletcher, Conley et al. 2011). The core hyper-arid region of the Atacama is located in the central depression between 24ºS and 25ºS at an elevation of about 1000 m.

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At these latitudes the high crestline of the coastal mountains blocks the marine layer fog from penetrating to the driest part of the Atacama Desert (Navarro-Gonzalez, Rainey et al. 2003).

Hyper-arid soils from this region are characterized by 1) extremely low levels of microorganisms (Navarro-Gonzalez, Rainey et al. 2003; Maier, Drees et al. 2004; Drees, Neilson et al. 2006; Connon, Lester et al. 2007; Lester, Satomi et al. 2007; Fletcher, Conley et Figure 4-6: The hyper-arid Atacama Desert has al. 2011), 2) low levels of organic material no visible primary producers through-out the (Navarro-Gonzalez, Rainey et al. 2003; hyper-arid core. Bagaley 2006; Drees, Neilson et al. 2006; Ewing, Sutter et al. 2006; Connon, Lester et al. 2007; Lester, Satomi et al. 2007; Valdivia- Silva, Navarro-Gonzalez et al. 2009; Valdivia-Silva, Navarro-González et al. 2011; Fletcher, Perez-Montaño et al. Submitted; Submitted) with only refractory organics present (Ewing, Sutter et al. 2006), and 3) the presence of an oxidant in the soil that is not chirally specific (Navarro-Gonzalez, Rainey et al. 2003; Quinn, Ehrenfreund et al. 2007).

It has been qualified as a Mars Analog for these characteristics (Navarro-Gonzalez and McKay 2011) as well as for geological (Heldmann, Conley et al. 2010) and mineral processes (Ewing, Michalski et al. 2007; Ewing, Amundson et al. 2008; Ewing, Macalady et al. 2008). Additionally, it has been used to test and qualify several Mars technologies and instruments including robotics (Wettergreen, Baulat et al. 1997; Cabrol, Wettergreen et al. 2007), the Mars Oxidant Analyzer for the Phoenix Mission (Skelley, Cleaves et al. 2006; Quinn, Ehrenfreund et al. 2007), and the Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory Mission (Mahaffy 2008).

All samples collected from this region are sands. A total of 7 samples were collected in 2006 that include beach sand, arid-region samples, and hyper-arid region samples. The distribution of these is shown in the Map as grey circles.

4.2.4. Atlas Mountains, Eastern Morocco

Morocco provides several good examples of terrestrial analogs to materials found on Mars including basic rocks and aqueous http://www.geomapapp.org altered minerals (Figures 4-1 & 4- Figure 4-7 2). A field expedition to this region in April of 2011 provided Erfoud the opportunity to collect samples Marrekech of materials for this project, gain a Basalt better understanding of the Quarzazate Limestone Ca-Carbonate processes that form these terrestrial analogs, as well as gain Stromatolite a better visual context of what these might look like on Mars.

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4.2.4.1. Travertines Travertines are a form of terrestrial limestone deposited by continental mineral springs and are formed by a process of rapid precipitation of Ca-carbonate minerals (e.g., aragonite, calcite, etc.) from solution in ground, surface waters, and/or geothermally heated hot-springs (Pentecost 2005). The specific mineral formed is dependent upon the temperature of the liquid medium. Current analysis of the geological history of Mars suggest that the processes which formed these materials on early Earth can provide an explanation for the formation of similar materials on Mars (Christensen, Bandfield et al. 2003). Certainly, thermal hot-springs on Mars are of particular interest in the search for life (Allen, Albert et al. 2000; Bishop, Murad et al. 2004). One sample was collected from the Quarzazate Travertine.

Figure 4-8: Field Expedition to the Kess Kess Devonian Mud Mounds in 2011 included 40 researchers with 11 support vehicles and drivers.

4.2.4.2. Carbonates The discovery of Carbonates on Mars (Morris, Ruff et al. 2010) by the Spirit Rover was an important moment as most of their terrestrial counterparts are formed as a result of a biogenic mediated aqueous process (Gabriele Ori, Cavalazzi et al. 2011). The increased understanding of how these might have been formed on Mars is important to understanding the habitability of early Mars. The Kess Kess Devonian mud mounds in the Eastern Anti-Atlas mountains (Figure 4-8) are expected to have formed in shallow water conditions and could be due to a baffling of sediments by marine grasses combined with an excess of carbonate produced by micro-organisms, or it could be due to hydrodynamic accumulation of mud produced by various algae and the breakdown of skeletal material (Gabriele Ori, Cavalazzi et al. 2011). Two samples were collected from this location. One is pure Calcium Carbonate while the other contains marine fossils embedded in the sample.

4.2.4.3. Stromatolite Fossilized Stromatolites from this location are nearly 600 million years old and have even been featured in the popular BBC program, First Life, hosted by Sir David Attenborough. There are no known instances of these organisms or fossilized structures being found on the surface of Mars; however, as these are also known to be a potential organism in the formation of carbonates, a sample of this was collected for use in the project.

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4.2.4.4. Basalt Figure 4-9 The Tinerhir site (Figure 4-9)consists of a small basaltic unit that expand within a large valley. The “flood basalt” has a source in a fault along the northern slope of the valley and occurs at the top of a dissected plateau. The unit is a prominent feature along the large valley west of Tinerhir and its color contrast with the predominant calcareous lithologies (Gabriele Ori, Cavalazzi et al. 2011). A sample of this was collected to use as an analog material for the formation of

planetary surfaces.

4.2.5. Rio Tinto, Spain

The Rio Tinto is situated in the Shale Jarosite South West of Iberian Spain within the Pyrite Belt Iberian Pyrite belt that has had Huelva continuously operating mining activities for nearly 5,000 years (Nocete, Figure 4-10 Alex et al. http://www.geomapapp.org 2005). The river maintains an acidic pH of about 2.3 for nearly the entire 100 km length. The pH of the water in the river is indicated by the color where as the pH drops to the most acidic conditions, the colors move from yellow to deeper red colors (Figure 4-11). Figure 4-11 Throughout the Rio Tinto river system, high concentrations of both iron and sulfates in a highly acidic aqueous environment form several types of iron-sulfate minerals including Jarosite (Rull, Fleischer et al. 2008). Jarosite from this location and the Rio Tinto have been qualified as Mars Analogs in the development, testing, and qualification of the Mars Organic Analyzer (MOA) which is a NASA-ESA jointly developed instrument on ExoMars (Skelley, Cleaves et al. 2006).

Two samples were collected during an expedition to this region in June of 2011 as indicated on the map. One is an early formation of Jarosite from the riverbed of the Rio Tinto. The second was shale formed under the local high acidic conditions.

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4.3. Analog Material Characterization

The material analogs for this project will be principally selected for use as spectral analogs, and characterization tests are designed to identify features and characteristics which could affect the spectral signature (Table 4-3). Except for IR diffuse reflectance, all other tests will be completed during Years 2 and 3 of the project. Methods and results of IR diffuse reflectance testing are discussed in the following sections.

Table 4-3: Characterization Tests for Material Analogs

Property Method Justification Chemical Mineralogy – Elemental SEM Specific mineral composition required in order to Composition ensure correct comparison of spectral signatures from other databases (ASU, RELAB, etc.) for similar material analogs and Mars remote sensing data. Physical Particle Size SEM/Aero-sizer These parameters can slightly change the spectral Particle Shape SEM measurement, so necessary for proper Relative Density TBD characterization. Total Density TBD Porosity TBD Water Content TBD Thermal Albedo TBD Necessary for comparison to Mars remote Physical Internal Thermal Inertia TBD sensing data. Spectral Diffuse Reflectance Mid/Near IR Principle measurement for characterization of material analogs which will be used for the determination of diagnostic bands necessary for bore-hole spectrometer as well as for comparison to data from other sources (ASU, RELAB, etc.).

4.3.1. Methods

4.3.1.1. Preparation of Samples

Several of the samples obtained for this project were in the form of rocks or large grain form. These included the Basalt, Gypsum, Limestone, Halite, and both the Jarosite and Ca- Carbonate samples. For the initial survey of mineral band positions, these needed to be prepared for spectral analysis by first grinding them into appropriate size fractions. Quantities of each mineral as collected were saved so that sensors will be able to be tested against the minerals in their natural forms.

Each sample was first cut into small pieces with a rock splitter (Figure 4-12A) and then passed through a rock crusher (Figure 4-12B) multiple times, closing the diameter of the throat with each successive pass until reaching the smallest throat size (Figure 4-12C). Because the grinder produces sand/dust size fractions during the grinding process, the ground material was passed through a 700 µm filter starting at the mid-range of the throat size. The <700 µm fraction was collected and stored in a plastic bag while, after the final pass, >700 µm fraction was stored in a separate plastic bag (Figure 4-12D)

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Figure 4-12: A) Rock Splitter, B) Split pieces fed through the grinder, C) Subsequent passes at smaller throat diameters, D) Final >700 µm and B <700 µm.

C D A >700 µm

Each sample was processed and stored separately. All equipment and machinery were <700 µm thoroughly cleaned with isopropanol in-between each sample in order to reduce cross sample contamination.

4.3.1.2. IR Diffuse Reflectance Characterization

Mid and Near IR Diffuse Reflectance were measured for each of the samples with a Bruker IFS 66v with a Specac Diffuse Reflectance jig installed in the sample measurement compartment. Mid IR range (300-7000 cm-1) was measured with a KBr beam splitter. The optics were set with the following settings: Detector Setting: DTGS; Scanner Velocity: 10kHz; Sample Signal Gain: 1; Switch Gain: Off. Prior to measurement of samples, a sample of KBr powder was used to calibrate the instrument by setting the gain to maximum amplitude of the KBr result. Post measurement, the drift during the testing was checked and pre-and post KBr spectra were averaged. Samples were loaded into a sample cup with the excess leveled with a wooden spatula (Figure 4-13). All samples were processed separately and individual spectra were normalized to the KBr calibration spectral result.

JSC SiO2 SiO2 Ca_Carb Basalt Gypsum Mars1 KBR Fisher Acros Limestone Ca_Carb W/Inclusions

Jarosite Jarosite Halite Montmorillonite Mojave Panoche Rio Tinto Figure 4-13 Sand

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4.3.2. Results and Discussion

Results of bulk Mid-IR Diffuse Reflectance testing (Figure 4-14) show significant variation across the variety of samples. Ideally, these will be separated out so that diagnostic features specific to a mineral type can be determined.

0.016

0.014 Figure 4-14

0.012

0.010 Single channel

0.008

0.006

0.004

0.002

0.000

7000 6000 5000 4000 3000 2000 1000 Wavenumber cm-1

As a preliminary analysis of the results, the spectral bands of the Quartz (Figure 4-15) and Ca-Carbonate Samples (Figure 4-16) match quite well with peaks at similar wave numbers. Differences are expected to be attributable to minor fluctuations of the instrument during testing, distribution of the particles within the testing cups, and some differences in the mineral composition. In particular, the Acros sample has a depressed peak in the 2800-2950 cm-1 range in comparison to the Fisher sample, and this might be due to the Fisher sample being a washed Sea Sand while the source of the Acros sample is unknown and could be from any number of pure quartz sources.

0.016

0.016 SiO2 Figure 4-15 Calcium

0.014 0.014 -1 Carbonate With Fossil

~2800-2950 cm 0.012

0.012 Inclusions

0.010

0.010 0.008

0.008 Figure 4-16

Single channel Single

Single channel Single

0.006

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0.000 7000 6000 5000 4000 3000 2000 1000 7000 6000 5000 4000 3000 2000 1000 Wavenumber cm-1 Wavenumber cm-1

C:\Documents and Settings\bowles\Desktop\spectrometer_readings_ian\Lauren\2011_07_25\20110725_1439_DM_FECA_CARBONATE_10MM_1600HZ_NOGAIN_200SCANS.02011/07/25 sample sample form C:\Documents and Settings\bowles\Desktop\spectrometer_readings_ian\Lauren\2011_07_25\20110725_1615_DM_FischerSiO2_Sand_10MM_1600HZ_NOGAIN_200SCANS.02011/07/25 sample sample form

C:\Documents and Settings\bowles\Desktop\spectrometer_readings_ian\Lauren\2011_07_25\20110725_1716_DM_Ca_Carbonate_10MM_1600HZ_NOGAIN_200SCANS.02011/07/25 sample sample form C:\Documents and Settings\bowles\Desktop\spectrometer_readings_ian\Lauren\2011_07_25\20110725_1655_DM_AcrosSiO2_Sand_10MM_1600HZ_NOGAIN_200SCANS.02011/07/25 sample sample form Page 1 of 1 Page 1 of 1

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On the other hand, in comparing the two 0.016 Jarosite 4400 3800 2400 1950

Jarosite samples (Figure 4-17), there are 0.014 1400 depressions in the Panoche sample at about 0.012 -1 Figure 4-17 1400, 1950-2400, and 3800-4400 cm . These 0.010

are beyond minor differences attributable to the 0.008 Single channel Single Rio Tinto above mentioned causes, and is more likely to 0.006

be due to mineral composition differences 0.004 Panoche

between the two samples where the Rio Tinto 0.002 0.000 Sample was taken as a fresh sample from the 7000 6000 5000 4000 3000 2000 1000 Wavenumber cm-1 center of the river bed and not fully formed C:\Documents and Settings\bowles\Desktop\spectrometer_readings_ian\Lauren\2011_07_26\20110726_1413_DM_Jarosite_Panoche_10MM_1600HZ_NOGAIN_200SCANS.02011/07/26 sample sample form

while the Panoche sample was taken from a C:\Documents and Settings\bowles\Desktop\spectrometer_readings_ian\Lauren\2011_07_26\20110726_1437_DM_Jarosite_RioTinto_10MM_1600HZ_NOGAIN_200SCANS.02011/07/26 sample sample form

sub-surface vein which could have had some Page 1 of 1 weathering over time.

Detailed analysis of these samples in comparison to both measurements made at other labs of similar materials (ASU, RELAB, JSC, etc.) and to Mars remote sensing data (OMEGA, CRISM, MER, etc.) will be made during the development of the project in years 2 and 3 in order to drive both the design of hardware as well as to ensure that all results are consistent with data from Mars Missions.

The goal of this analysis will be to create a chart of spectral bands which could be used as diagnostic features to discriminate one mineral from another. This approach was taken by Anderson et al. (2005) at JPL who determined the spectral bands (Figure 4-18) for a set of analog minerals and compounds for use with a proposed in situ Fourier Transform Infrared Spectrometer for Mars exploration. From this analysis, spectral frequencies necessary for selection of filters will be determined. Band-depth ratios and other spectral relationships can be identified which are specific to a mineral as other secondary approaches to mineral discrimination. This work and the work of Anderson indicates that an IR Filter- Radiometer may be a suitable solution for this instrument. Future work will be for the Figure 4-18: Spectral bands for a variety of minerals development of this type of system. and compounds for an in situ Mars FTIR spectrometer (Anderson et al. 2005).

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5. Sensor Development Testing

5.1. Parameters and Ranges

In the previous section, parameters were identified for measurement in order to satisfy the hypothesis. These included the presence of water (liquid, ice or vapor), an energy source (chemical from a mineral), and nutrients for cellular material, all under inclement conditions allowing for a liquid medium (even if the conditions only occasionally allow a liquid form).

During the Mars Phoenix Mission, subsurface water ice on Mars was shown to pass directly to vapor (Smith, Tamppari et al. 2009) and even to reach liquid form (Renno, Bos et al. 2009). Temperatures have also been shown to reach nearly 27°C (300K) at Mid-latitudes of the surface (Carr 1996) which is warm enough for liquid pure water which has a freezing point of 0°C (273K) and cryo-brines, depending on the composition of the salt, with freezing points as low as -79°C (194K) (Möhlmann 2009). Trapped, sub-surface water ice is exposed to the heat of the drilling process (Zacny 2004) as well as the atmosphere in an open bore- hole. Both processes will cause trapped sub-surface ice to pass to vapor form and which will increase the RH within the bore-hole. For this reason, RH was chosen as one of the parameters to measure as an indicator for the presence of water.

Because this project will be utilizing Analog Natural Environments, two have been selected which give the widest range of RH and Temperature parameters. These are the Atacama Desert as a hyper-arid hot desert and the Antarctic Dry Valleys as a hyper-arid cold desert. The range of temperatures and RH in these three environments are listed in Table 5-1 for both surface and subsurface (when known).

Table 5-1: Range of Environmental Parameters in Analog Environments and on Mars

Environment Temperature Range* (°C) RH Range* (%) References Atacama Desert (McKay, Friedmann et al. (Yungay): -5.7 to 32 8 to 75 2003; Warren-Rhodes, Surface (Atmosphere) < 0 to 50 (@10cm) 5 to 45 (@10 cm) Rhodes et al. 2006; Subsurface (depth) Davis, de Pater et al. 2010) Antarctic Dry Valleys Mckay et al. (1998; 2009) (Linneaus Terrace): Surface (Atmosphere) -42.6 to -3.8 15 to 95 Subsurface (depth) -40.2 to -2.4 (@17cm) Up to 100% at @ ice interface Mars: Mid-Latitudes (Carr 1996; McKay, Surface (Atmosphere) -90 to 25 TBC Mellon et al. 1998; Subsurface (depth) -60 to -55 (@15 cm) Up to 100% at @ ice McKay, Molaro et al. interface 2009) *Note: These are typical ranges, and these values can be exceeded on rare occasions.

Temperature measurement is important for calculating the capability for liquid water, but it is also necessary in order to adjust the measurement of the Relative Humidity sensors. The range of temperatures required to measure is based upon the minimum temperatures to be seen on Mars at the surface (atmospheric) and the maximum likely to be seen at the surface of the Atacama (0 cm depth). This results in a temperature range of -90 to +50 °C. This is a reasonable first pass at a setting the required temperature range because subsurface

37 Fletcher Year 1 Report Rev: Final

temperatures on both Mars and the Antarctic are much higher than the low end range and because surface temperatures (atmospheric) on Mars will never reach the high end.

The RH range requirement can be established from a similar analysis. The minimum RH is established by the measured RH in the subsurface of the Atacama Desert, and the maximum is based upon the knowledge that at an ice-soil boundary, the RH is at the maximum of 100% (McKay, Molaro et al. 2009). This results in an RH range of 5 to 100%.

Additional requirements will be established in the next phase of development, and these will include, at a minimum, sensitivity, drift, repeatability, stability, and power.

Sensors selected for preliminary testing included two temperature sensors and two RH sensors. The principle purpose for these sensors were to serve as sensors for the development of the science, methods, supporting hardware (including micro-control and data acquisition systems and simulated environment systems), engineering models, and protocols. The HUMICAP flight instrument for the measurement of RH and temperature is too bulky for bore-hole use; however, these sensors as tested have the right size and power consumption for a PCB mounted bore-hole instrument and will have further testing to determine if they are appropriate for use in this project. A method and sensor for the determination of material types was not selected for preliminary testing at this stage of the development of the project and will be investigated and developed as part of Years 2 and 3.

5.2. Temperature Testing A Resistance Temperature Device (RTD) was selected for initial temperature measurement for this project. The sensor selected was a Sensing Devices LTD (SDL) Pt100 RTD (P/N: 15E) (http://www.sensing-devices.co.uk/). This is a platinum wire wound device with a ceramic tube exterior in which the resistance changes as a function of the temperature. The dimensions of the device are 15mm by 0.78 mm (diameter). Additional specifications and range of operation of the device are unavailable at this time. The device was set up with a four-wire connection.

The device was calibrated with standard methods. The sensor was immersed in an ice-point cell with no attempt to heat sink the sensor to the working fluid. The excitation current was at 25 Hz. The measured Ro values were 100.0636 @ 0.22 mA and 100.0665 @ 0.73 mA. Unfortunately, the sensor was damaged beyond repair during installation of subsequent RH testing, so calibration curves for this specific device are not presented here. Subsequent RTD sensors will be calibrated following these methods.

5.3. Relative Humidity Testing Two types of capacitive sensors were selected for initial RH measurement for this project. This sensing method is a reasonable choice for initial testing as it is being used for the ExoMars MiniHum RH sensor (Koncz, Lorek et al. 2007).

The first RH sensor selected was a Honeywell HIH-4000-004 (http://sensing.honeywell.com). This device is a laser trimmed, thermoset polymer capacitive sensor with on-chip integrated signal conditioning. Thermoset polymer-based capacitive RH sensors directly detect changes in relative saturation as a change in sensor capacitance. Relative saturation is the same as ambient relative humidity when the sensor is at ambient temperature so that a change in capacitance is a measure of the RH change. The dimensions of the 3-pin packaging are

38 Fletcher Year 1 Report Rev: Final

4.2x8.6x2.0 mm. The device is driven with a 5VDC drawing 200 mA, with the center pin as the output voltage for reading the capacitance value and which can be calibrated to the RH. The typical response of the device (Figure 5-1A) demonstrates good linearity with a typical 0% RH off-set voltage of about 0.83 V and 100% RH topping out at about 3.8 V. While the operational temperature range of the device is -40°C to 85°C, the operational life-cycle has a reduced range (Figure 5-1B) where low end temperatures reduce the recommended RH operational range. This could be problematic in both the Antarctic and Mars settings which have lower temperatures and could have nearly 100% RH at the ice-soil boundary.

B

A

Figure 5-1: A) Honeywell technical data sheet calibration curve for a typical HIH-4000-004 device at 25°C and 5VDC input. B) Recommended operational ranges for temperature and RH (Honeywell 2008).

The second RH sensor selected was an Innovative Sensor Technology (IST) P14 Thermo Capacitive Humidity and Temperature Sensor (www.ist- ag.com). This is an integrated device with both a Pt100 RTD and a P14 RH Sensor in one package. The P14 is a capacitive RH sensor constructed by depositing a thin film polymer between two conductive electrodes on a ceramic substrate. The sensing surface is then coated with a microporous metal Figure 5-2: Diagram of the circuit used to power and measure the electrode that allows the polymer capacitive change in the P14 RH sensor (IST 2009). to absorb moisture. As the polymer absorbs water, the dielectric constant changes incrementally such that a change in the capacitance is a measure of the RH change. The Pt100 RTD operates the same as previously described. The dimensions of the four electrode Surface Mount Device (SMD) is

39 Fletcher Year 1 Report Rev: Final

6.4x2.3x0.4 mm. The device is driven by a 2.5 VDC converted to an alternating signal (<12 Vpp AC max) without DC bias, via a 7556 dual timer IC (Figure 5-2). As the capacitance across the P14 change due to changes in RH, the 7556 converts this to a DC output voltage which can be calibrated to the RH. The RTD side of the sensor was set up with a four-wire connection, but was not calibrated at this time. The typical response of the device (Figure 5- 3A) demonstrates good linearity. The operational temperature range of this specific model is - 50°C to 150°C, though above 85°C, there is a significant drop-off in the RH range (Figure 5- 3B). The low end temperature range does not suffer from the same limitations as the Honeywell HIH-4000-004 and has full RH range to the lowest specified operational temperature of -50°C.

Capacitance (pF) Capacitance

A

RH (%)

B

RH(%)

Temperature (°C)

Figure 5-3: A) IST technical data sheet calibration curve for a typical P14 device at 23°C. B) Recommended operational ranges for temperature and RH (IST 2009).

Of special note is that IST sells a P14 RH sensor without the integrated Pt100 which has a specified temperature range of -80°C to 150°C. It would appear that the IST P14 RH only device may have the capability for immediate use in the full Antarctic and Mars ranges of RH and Temperature. Because of this, it will likely be selected for future testing in Years 2 and 3 with a separate Pt100 selected for temperature measurement and compensation.

40 Fletcher Year 1 Report Rev: Final

5.4. Calibration of RH Sensors A two-point method of 0% RH and 100% RH was developed for in-house calibration of these sensors. The calibration curve of a typical HIH-4000-004 sensor was provided as part of the technical documentation for this sensor (Figure 5-1). The calibration is run at 25°C, so this was the set-point for the in-house calibration in order to be able to compare results to the typical curve. A double container system was developed with a sealed metal electrical box as the inner container and a Styrofoam shipping container as the outer (Figure 5-4). Pass- through holes were placed in each container for electrical wiring and a dry-nitrogen line into the inner container). The inner volume was not fully sealed such that air and nitrogen would escape through the electrical wiring hole. Electrical circuits were built on a solder less breadboard which was placed outside of the outer container. An HP/Agilent digital voltage supply provided the 5VDC and 2.5VDC required. An Agilent 34970 with 34974 multiplexer was used for data acquisition. The Agilent 34970 converts a four wire RTD input directly to temperature (°C) without any further electronics. An external PC interfaced to the Agilent 34970 recorded the data. Temperature control was maintained at 25°C by the Air Conditioning unit of the Temperature Calibration Lab where the calibration tests took place. The 0% RH point was obtained by placing the sensor within the inner volume and closing the outer volume and then feeding dry-nitrogen into the inner volume until the reading stabilized at the lowest voltage (Figure 5-5B). Because nitrogen being feed into the inner volume was assumed to push out the original air until only nitrogen was left, this was considered to be the 0% RH state. The 100% RH point was obtained by placing an open dish of distilled water into the inner volume and closing the lids of both the inner and outer volume. Over time, the inner volume air would evaporate the water in the dish until fully saturated and the reading at the maximum voltage was considered to be the 100% RH state (Figure 5-5A). The final RH sensor may need independent calibration by an outside lab.

9 4 B 6 7 3 5

2 10 9 8 1 A C

Figure 5-4: A) Experimental set-up for calibrating the RH sensors. B) 0% RH configuration with Nitrogen Line installed. C) 100% RH configuration with open water dish. Specific Components are as Follows: 1) Inner Container, 2) Outer Container, 3) HP Digital Voltage Supply, 4) Agilent 34970 DAQ, 5) PC Control System, 6) External control circuit boards, 7) Nitrogen Line, 8) Water Dish, 9) Wiring Pass-through holes. 10) HIH-4000- 004 RH Sensor.

41 Fletcher Year 1 Report Rev: Final

Initial calibration testing of the two RH sensors shows the sensor responses to changes in RH concentrations are nearly identical. The Dynamic range of the Honeywell device would appear to be much greater, but this is because the output of the IST device is through the 7556 and a high pass filter which chops it to a DC output signal and reducing the observable range. The manufacturers curve for this device (Figure 5-5C) actually shows a much better dynamic range across the capacitance as opposed to the DC output generated by this specific circuit. Because the operational range of the IST device is significantly better, future work on the specific measurement circuit will be required.

4.5 100% RH Cal Test A 3 B 4 0% RH Calibration 2.5 100% RH Within Control Ambient RH 3.5 Volume (4.06VDC) 2 (1.98 VDC) 3 IST-P14 RH 0% RH

VDC 1.5

Honeywell: HIH-4000-… VDC (1.34 VDC) 2.5 Ambient RH 1 (1.42 VDC) 2 Ambient RH (1.98VDC) 0% RH 0.5 1.5 (0.83 VDC) (1.65VDC) (1.40VDC) 0 1 17:21:0717:22:3417:24:0017:25:2617:26:53 17:34:05 17:48:29 18:02:53

Figure 5-5: A) Results of the 100% RH state, B) Results of the 0% RH State, C) Two point calibration curve of the two sensors.

C 4.5 RH Sensor Calibration Curve 4 (Two Point: 0% & 100%) 3.5

3

2.5

VDC 2

1.5

1 IST-P14 0.5

0 0 10 20 30 40 50 60 70 80 90 100 RH (%)

42 Fletcher Year 1 Report Rev: Final

6. Forward Work Plan

The continued development of this project will be tied to the development of the dissertation. The proposed chapters are as follows:

1. Introduction and Background including the subsurface of Mars 2. Previous work and development of the Hypothesis 3. Analog Materials, selection and characterization 4. Sensor selection, testing, characterization and integration 5. Laboratory Testing, individual sensors and integrated package 6. Field Testing 7. Application to Mars sub-surface environment 8. Conclusions and further work

To summarize the work of the previous sections of this report, a brief overview of previous missions was presented including scientific results relevant to the sub-surface environments of this project and what is missing from these previous missions as well as upcoming missions. This was followed by a discussion of the history of the exploration of Mars prior to the modern space age which provides the fundamental motivation for this project (“Where did we come from?”, “Are we alone in the universe?”, and “What is our future beyond the Earth?”) and ended with the establishment of the central hypothesis of the project: The subsurface environment of Mars provides habitable conditions sufficient to support life.

It continued with defining the fundamental concepts of Life and Habitable and provided a list of questions which must be answered in order to quantify a habitable environment on Mars and suggested specific measurements for this purpose.

The discussion continued with an explanation of the need for the use of analog materials and simulated and 6 natural analog environments for the testing and qualification of hardware developed as part of this project. Materials were selected, collected, 1 and initial characterization of these 5 were completed. The final section reported on sensors necessary for the measurements to quantify 4 habitability and presented data on the 2 initial testing and characterization of 3 two RH and two temperature sensors (Figure 6-1) Figure 6-1: Sensors, mBed microcontroller, and sub-surface This work forms the bulk of the probe prototype. 1) PE Thermopile, 2) IST RH, 3) Sensing material needed for Chapters 1-3 and Devices Pt100 RTD, 4) Honeywell HIH-4000-004 RH, 5) mBed microcontroller, 6) Prototype sub-surface probe starts in on Chapter 4. While additional work to flush out and complete Chapters 1-3 is anticipated, the future work of this project in Years 2 and 3 will start with Chapter 4 and continue from there.

43 Fletcher Year 1 Report Rev: Final

Selection of sensors for Chapter 4 is the first task. An RH and Pt100 sensor have already been initially tested and additional testing will continue under simulated Mars environmental conditions. These are expected to perform as required and will most likely be selected for the final integrated design. If they do not pass testing, there are several other manufacturers that can provide substitutes or it may be possible to switch to using a water band on the spectral sensor as the principle means of detection of water vapor.

An Infrared Filter-Radiometer was proposed as the means for the detection and discrimination of minerals (Section 4.3.2). This is the same approach as is done for both Themis and the Lunar Diviner missions, and from the work in Section 4 of this report and by the work of Anderson et al. (2005) at JPL, this is a reasonable approach as the purpose of this sensor is not as a general survey instrument, but rather, to discriminate specific mineral types and/or classes which have already been identified as part of Chapter 3. A Perkin Elmer Cool Eye thermopile 2x8 array has been selected for initial testing and development and which will be supported by an mBED microcontroller (Figure 6-1). A block diagram of the functional system is provided in Figure 6-2. The device has the capability for installing different filters over each pixel and is temperature compensated. The over-all dimensions are 25x17x8mm for the Cool Eye and 25x45x10mm for the Mbed which make them both good first choices for a subsurface integrated system with a requirement to be less than 30mm (diameter).

Figure 6-2: Functional block diagram PC of integrated system. (Serial)

PWM RH input Din IR Sensor

mBed Microcontroller RH (Arm Cortex 3)

Analog in

MUX (Based on TDS)

PRT Temp. Possible Environ. House- Pressure Keeping Sensor

44 Fletcher Year 1 Report Rev: Final

Major tasks for the radiometer development and final selection are as follows:  Characterization of the detector by testing under a 500K blackbody with the Diviner filter set. o Determine the D* value o Confirm the manufacturers reported values o Determine drift and repeatability across the 2x8 array . Determine the signal to noise performance o Measure the spectral response via the Bruker spectrometer . Determine the low-end cut-off of integrated system  Synthetic Calculations o Use emissivity spectra from analog materials o Develop diagnostic method for discrimination of minerals o Compare drift and signal to noise ratio

The results of this testing are expected to: 1) Determine if the integrated system works as required 2) Determine the filter set 3) Determine the integration time 4) Characterize the general performance 5) Determine the calibration scheme

Given successful completion of this round of testing, the final product of this phase will be a CAD design of the integrated radiometer. This phase of testing is expected to be completed in the next 60-70 days in order to allow for the following work to take place in a reasonable time frame associated with a D.Phil project.

Chapter 5 will comprise the major laboratory testing of the individual sensors and the integrated design to include calibration and operation under simulated Mars environmental conditions. Given successful completion of this testing, the final integrated design will be tested to raise it to a Technology Readiness Level (TRL) of 5 with additional flight qualification tests of vibration and shock, thermal cycling, and others as appropriate.

Chapter 6 will comprise the operation of the integrated system in situ in natural Mars analog environments. These locations will include the Atacama Desert (Peru: TBC, or a substitute as necessary) and the Dry Valleys of Antarctica (already scheduled for the 2012-13 field season). This Antarctica field testing will be in collaboration with the IceBite drilling team in order to take bore-hole measurements with the device in development by Honeybee and NASA.

Chapters 7 and 8 will place these devices in the context of Mars and recommend further work as appropriate in order to raise the instruments from TRL 5 to TRL 8. Completion of the project is anticipated as August 2013. The projected timeline is provided in the following gantt chart.

45 Fletcher Year 1 Report Rev: Final

46 Fletcher Year 1 Report Rev: Final

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Appendix A: Table of Material Analogs

Sample Location GPS Coordinates Description Note References Ca-Carbonate Morocco 31° 22.791‟ N Kess Kess Mud Morris et al. (2010) 04° 01.894‟ W Mound Ca-Carbonate Morocco 31° 22.724‟ N Kess Kess Mud Morris et al. (2010) 04° 01.905‟ W Mound w/fossil inclusions Basalt Morocco 31° 26.010‟ N Pure flow Rieder (2004) 05° 09.034‟ W Gypsum Pomaia, Italy 43° 25‟ 23.75” N Wards P/N: 46E 3783 Gendrin (2005) 10° 33‟ 19.09” E Limestone Morocco 30° 59.365‟ N Morris et al. (2010) 06° 41.972‟ W Halite Hampton 42° 44‟ 49.25” N Wards P/N: 46E 3828 Bridges & Grady (1999) Corners, NY 77° 58‟ 13.73” W Rieder (2004) Jarosite Panoche Hills, 36° 37‟08.18 N Pure vein from sub- Golden et al. (2008) CA 120° 39‟ 15.98” surface sample W Jarosite Rio Tinto, 37° 37‟ 39.90 N River bed sample Golden et al. (2008) Spain 6° 32‟ 10.78” W Hematite Republic, 46° 23‟ 45.75” N Wards P/N: 46E 3875 Christensen et al. (2001) (Micaceous) Michigan 87° 58‟ 19.79” W Quartz N/A N/A Fisher P/N: S25-3 Bandfield (2002) Quartz N/A N/A Acros P/N: S24/25 Bandfield (2002) JSC Mars-1 Pu‟u Cinder 19° 43‟ 14.13” N Orbitec Allen et al 1998 Cone, Saddle 155° 28‟ 19.54” Road, Island W of Hawaii Montmorillonite Fowlkes Mine, 33° 45‟ 09.29‟ N Wards P/N: 46E 0435 Bishop(1993) Panther Creek, 88° 31‟ 43.49” W Miss. Mojave Sand Little Red Hill, 35° 22‟15.22” N Arid environment Allen et al. (1998) CA 116° 09‟ 48.06” Fletcher et al., 2011 a & b W Serpentine Wards Shale Rio Tinto, 37° 43.276‟ N Next to river bed Spain 006° 33.767‟ W Stromatolite Morocco 30° 47.625‟ N 600MYr old fossil 006° 43.319‟ W Atacama Sand: Yungay, Chile 24° 1.437‟ S Hyper arid sample. Allen et al. (1998) AT05-44 69° 52.169‟ W Fletcher et al., 2011 a & b Atacama Sand: El Cobre 24° 16‟ 39.4” S Pure beach sand Allen et al. (1998) ATLF05-56 Beach, Chile 70° 31‟39.7” W Fletcher et al., 2011 a & b Atacama Sand: Chile 24° 17‟ 17.6” S Canyon from El Cobre Allen et al. (1998) ATLF05-59A 70° 30‟53.9” W Beach to Yungay. Arid Fletcher et al., 2011 a & b environment. Atacama Sand: Yungay Basin, 24° 05‟ 48.52” S Entry to hyper-arid Allen et al. (1998) AT05-107-1 Chile 70° 16‟44.22” W basin from beach road Fletcher et al., 2011 a & b Atacama Sand Yungay Basin, 24° 03‟ 51.56” S Hyper-arid basin in Allen et al. (1998) ATCC05-169 Chile 69° 53‟43.35” W run-off Fletcher et al., 2011 a & b Atacama Sand Yungay Basin, Hyper-arid basin Allen et al. (1998) ATCC05-183 Chile outside of run-off Fletcher et al., 2011 a & b Atacama Sand: Yungay, Chile 24° 04.206‟ S Center of rock garden, Allen et al. (1998) CC-05, Rock 69° 51.994‟ W hyper-arid Fletcher et al., 2011 a & b Garden

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Appendix B: List of Other Analogs in Figures 4-1 & 4-2

Sample Symb. Location: Earth Location: Mars Comments References Travertine and Limestone Mammoth Formation & Gusev Crater Hydrated altered materials Bishop et al. (2004) Octopus Springs, Yellowstone National Park, WY, USA Palagonite Etna Volcano, Italy General Spectral Alternative to JSC Mars-1 from Hawaii Esposito et al. (2000) Skeiðara´rsandur, Iceland Warner & Farmer (2010) Montmorillonite N/A Wyoming Syria & Lunae Planum Wards Esposito et al. (2000) Andesite N/A Colorado Various Wards Esposito et al. (2000) Felsic Volcanics Skeiðara´rsandur, Iceland Various Including Andesite, dacites, and rhylites. Warner & Farmer (2010) Basalt Skeiðara´rsandur, Iceland Meridiani Planum Warner & Farmer (2010) Craters of the Moon Lava Gusev Crater Cornell & Hausrath (2010) Field, Idaho, USA Albite N/A Skeiðara´rsandur, Iceland Various Warner & Farmer (2010) Quartz N/A Skeiðara´rsandur, Iceland Various Warner & Farmer (2010) Zeolites N/A Skeiðara´rsandur, Iceland Various Warner & Farmer (2010) Beidellites N/A N/A Various Bishop et al. (2010) Calcium Carbonate Phoenix Lander Boyton et al. (2009) Sulfates (altered) Dixie Valley, NV, USA Various Ca, Si, & Al-sulfates Housrath (Hausrath 2010) Labradorite/Halite N/A N/A N/A Reagent grade halite Jensen & Glotch (2010) Na-Sulfate Lewis Cliff Ice Tongue, Various Liu and Bish (2010) Antarctica Na-borate Lewis Cliff Ice Tongue, Various Liu and Bish (2010) Antarctica Na-bicarbonate Lewis Cliff Ice Tongue, Various Liu and Bish (2010) Antarctica Ca-Sulfate Cerro Negro Volcano, Various Marucci et al. (2010) Nicaragua Carbonates Spitzbergen, Norway Various McAdam et al. (2010) Jarosite Olduvai Gorge, Tanzania Various McHenry et al. (2010) Ferrer Dolerite Becon Valley, Antarctica Various Salvatore et al. (2010) Note: This is just a general survey of the breadth and depth as there are a significant number of papers in the last 10 years analyzing Terrestrial Analogs and comparing them to recent reported discoveries from the various Mars missions

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