Impacts of Sieving and Cultivation on Martian Regolith Simulant By

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Impacts of Sieving and Cultivation on Martian Regolith Simulant

By Abdulgadir Ahmad Elnajdi

Bachelor of Science, Omar Al Mukhtar University, Libya

A thesis

Submitted to the Department of Chemistry - Florida Institute of Technology

In partial fulfillment of the requirements for the degree of

Master of Science

Biochemistry

Melbourne, Florida

May, 2018

Impacts of Sieving and Cultivation on Martian Regolith Simulant

By Abdulgadir Ahmad Elnajdi

A thesis by

Abdulgadir Ahmad Elnajdi

Approved as to style and content

______

Mary L. Sohn, Ph.D., Committee Chairperson

Professor, Department of Chemistry

______

Alexander Schoedel, Ph.D.

Assistant Professor, Department of Chemistry

______

Richard B. Aronson, Ph.D.

Professor, Department of Biological Sciences

Abstract

Title: Impacts of Sieving and Cultivation on Martian Regolith Simulant

Author: Abdulgadir Ahmad Elnajdi

Major Advisor: Dr. Mary Sohn

The effect of different size particle fractions of JSC-MARS1A on chemical and mineralogical data was examined in this study. The Powder X-ray Diffraction

(PXRD) and Scanning Electron Microscopy (SEM) results showed no difference in the presence of elements or minerals of the different grain sizes of (<5mm, <1mm,

<125µm, and <63µm), however, differences in abundance were noted. In addition, changes in chemical composition and mineralogy were not detected after the addition of Hoagland’s nutrient solution which had been applied prior to plant growth experiments nor after plant growth.

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Table of Contents 1- Introduction ...... 1 1.1- Martian Regolith...... 3 1.1.1- Mineralogy...... 3 1.1.2- Chemical Composition...... 3 1.1- JSC Mars-1A Simulant Mineralogy and Chemical Composition...... 5 1.3- The Geological History of Earth and Mars...... 6 1.4- Effects of Nutrient Supplements on the Mineralogical and Chemical Composition of JSC Mars 1A...... 10 2- Materials and Methodology ...... 11 2.1- Materials ...... 11 2.2- Analytical Methods ...... 11 3- The Chemical Composition and Mineralogy of JSC MARS 1A after a Growth Experiment on Simulant...... 15 4- Results and Discussion...... 16 4.1- Elemental Composition ...... 16 4.2- Correlation of Elemental data with Mineralogy...... 20 5 - Effects of Nutrient Supplements on the Mineralogical and Chemical Composition of JSC Mars 1A...... 40 6- Summary ...... 45 7- References...... 47 APPENDIX A ...... 51 APPENDIX B ...... 52 APPENDIX C ...... 53 APPENDIX D ...... 55 APPENDIX E ...... 62

List of Figures

Figure 1: Martian regolith simulant ...... 2 Figure 2: Comparison of the geological timescales for Mars and Earth. (Scott M. Mclennan, 2012) ...... 7 Figure 3: X-ray spectra collected by SEM for grain sizes <5mm and <63µm……...... 19 Figure 4: SEM images of the morphology of JSC MARS 1A ...... ……………………..19 Figure 5: Compositional image and x-ray mapping of the cross sections of JSC MARS 1A, grain size <5mm ...... 21 Figure 6: Compositional image and x-ray mapping of the cross sections of JSC MARS 1A, grain size <63µm ...... 21 Figure 7: The observed pattern for grain sizes (<1mm) versus the Albite database...... 23 Figure 8: The observed pattern for grain sizes (<5mm) versus the Albite database...... 23 Figure 9: The observed pattern for grain sizes (<63µm) versus the Albite database ...... 24 Figure 10: The observed pattern for grain sizes (<125µm) versus the Albite database ...... 24 Figure 11: The observed pattern for grain sizes (<1mm) versus the Andesine database ...... 25 Figure 12: The observed pattern for grain sizes (<5mm) versus the Andesine database ...... 25 Figure 13: The observed pattern for grain sizes (<63µm) versus the Andesine database ...... 26 Figure 14: The observed pattern for grain sizes (<125µm) versus the Andesine database ...... 26 Figure 15: The observed pattern for grain sizes (<1mm) versus the Anorthite database...... 27 Figure 16: The observed pattern for grain sizes (<5mm) versus the Anorthite database ...... 27 Figure 17: The observed pattern for grain sizes (<63µm) versus the Anorthite database ...... 28 Figure 18: . The observed pattern for grain sizes (<125µm) versus the Anorthite database...... 28 Figure 19: The observed pattern for grain sizes (<1mm) versus the bytownite database...... 29

Figure 20: The observed pattern for grain sizes (<5mm) versus the bytownite database ...... 29 Figure 21: The observed pattern for grain sizes (<63µm) versus the bytownite database ...... 30 Figure 22: The observed pattern for grain sizes (<125µm) versus the bytownite database ...... 30 Figure 23: The observed pattern for grain sizes (<1mm) versus the Labradorite database ...... 31 Figure 24: The observed pattern for grain sizes (<5mm) versus the Labradorite database ...... 31 Figure 25: The observed pattern for grain sizes (<63µm) versus the Labradorite database...... 32 Figure 26: The observed pattern for grain sizes (<125µm) versus the Labradorite database...... 32 Figure 27: The observed pattern for grain sizes (<1mm) versus the Oligoclase database ...... 33 Figure 28: . The observed pattern for grain sizes (<5mm) versus the Oligoclase database ...... 33 Figure 29: The observed pattern for grain sizes (<63µm) versus the Oligoclase database ...... 34 Figure 30: The observed pattern for grain sizes (<125µm) versus the Oligoclase database...... 34 Figure 31: The observed pattern for grain sizes (<1mm) versus the Maghemite database ...... 35 Figure 32: The observed pattern for grain sizes (<5mm) versus the Maghemite database ...... 35 Figure 33: The observed pattern for grain sizes (<63µm) versus the Maghemite database ...... 36 Figure 34: The observed pattern for grain sizes (<125µm) versus the Maghemite database...... 36 Figure 35: Structural and magnetic transformation of np iron oxide/oxyhydroxide deposited on clay...... 39 Figure 36: Compositional image and x-ray mapping of the cross sections of JSC MARS 1A Mixture (<1mm and <5mm) ...... 41 Figure 37: Compositional image and x-ray mapping of the cross sections of JSC MARS 1A Mixture (<1mm and <5mm) after adding nutrient supplements and crop growth...... 41 Figure 38: PXRD data for identified minerals in Mars regolith simulant ...... 46

List of Tables

Table 1: Major elemental composition of Martian soil (wt. %) ...... 4 Table 2: Chemical Composition of JSC-Mars-1A ...... 5 Table 3: Comparison of selected common sedimentary mineralogy observed on Earth with known mineralogy on Mars with idealized chemical formulas1 ...... 9 Table 4: Grain Size Distribution of JSC Mars 1A <5mm Sample ...... 12 Table 5: Minerals that were included in the EVA software for possible detection by Powder X-ray Diffraction ...... 13 Table 6: The number of databases that both positively and negatively identified each mineral ...... 17 Table 7: The elementary composition of the JSC Mars A1; <5mm and <63µm ..... 18 Table 8: Minerals identified in Mars regolith simulant...... 37 Table 9: Composition of the plagioclase minerals...... 38 Table 10: Elemental Composition (weight %) of JSC Mars 1A mixture (<1mm and <5mm) ...... 43 Table 11: Elemental Composition (weight %) of JSC Mars 1A mixture (<1mm and <5mm) after growing crops ...... 44

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Acknowledgements.

Many thanks to my advisor Professor Mary Sohn for her exemplary guidance and encouragement throughout the project. Special recognition to the thesis committee members Assistant Professor Alexander Schoedel and Professor Richard B.

Aronson. Thank you to Dr. Palmar and his research team “RADISH” for providing treated soil samples with the nutrient supplements. Lastly, to my colleagues and school partners with the continuous support throughout my master’s program.

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1- Introduction

Progress in determining the geological history of Mars is derived from measurements conducted on the surface of the planet by robotic measuring devices launched by NASA and other space agencies (Inge L. ten Kate, ASCE 2013). This information has helped scientists identify soil on the Earth's surface similar to the

Martian soil and much of the discussion of the chemical composition of Martian regolith is focused on palagonite (J. R. Michalski, 2005). Palagonite is the first stable product of volcanic glass alteration and is typically composed of an amalgamation of all or some of the following materials: residual basaltic glass, zeolites, carbonates, phosphates, hematite, Fe-hydroxides, poorly crystalline aluminosilicate mineraloids, and smectite clays (J. R. Michalski 2005). The regolith simulant used in this study, JSC MARS-1A, consists of palagonitic tephra from Pu’u

Nene in Hawaii which NASA believes to be a very representative sample of Martian regolith. Hawaii and Mars both exhibit a history of volcanism. The volcanic deposits in the Ka’u desert, Kilauea Mauna Loa and Manua Kea provide a range of useful chemical analogues showing significant similarities to regional soils on Mars

(Carlton C. Allen, Karen M. 1998). Weathered ash from the Pu’u Nene cinder cone in Hawaii is the source of the JSC MARS-1A sample. This Martian regolith simulant was collected and characterized by scientists and engineers at Johnson Space Center in 1993 (Figure1). Interestingly, the study of Hawaiian geology and Martian climate

1 led some researchers to predict the presence of kaolinite on Mars, a prediction that has recently been shown to be true, indicating weathering of igneous rocks to form clays (Karsten Seiferlin, 2008).

Figure 1 –A. JSC Mars 1A Figure 2- B. JSC Mars 1A Powder Microscopic Image

Figure 1-C; back scattered electron images of JSC-Mars 1A

Figure 1: Martian regolith simulant

1.1- Martian Regolith.

Martian regolith is characterized by a varied composition including reaction products from interaction with volcanic gases, especially SO2 and HCl, mechanically mixed and distributed on a global scale by dust storms. The felsic components have high SiO2, high K, but low Mg contents. The Martian regolith also contains basaltic components similar to the composition of basaltic rock found on Earth on the

Hawaiian Island chain.

1.1.1- Mineralogy.

Data from ground-based landers/ rovers and orbital spacecraft revealed that the Martian surface is dominated by basaltic regolith composed primarily of pyroxene, plagioclase feldspar, and olivine as well as minor amounts of Fe and Ti oxides (Yen et al. 2005 Morris et al 2006a; Morris et al. 2006b; McSweeen et al.

2010; Bish et al. 2013).

1.1.2- Chemical Composition.

Martian surface regolith measured by the Viking Landers, Pathfinder, Spirit,

Opportunity, and Curiosity show that the bulk of the chemical composition of these materials is relatively constant at widely spaced locations across the planet (Table 1)

(Allen C. C. 1998). Data from these locations are essentially identical, suggesting that the regolith has a component which is distributed planet- wide, probably by the wind (Toulmin et, al, 1977).

Table 1: Major elemental composition of Martian soil (wt. %)

aBanin et al. (1992). bFoley et al. (2003). cGellert et al. (2004). dRieder et al. (2004). eBlake f g et al. (2013). Taylor and Mclennan (2009). Peters et al. (2008).

1.1- JSC Mars-1A Simulant Mineralogy and Chemical Composition.

According to NASA Johnson Space Center, JSC Mars-1A is an altered volcanic ash mainly composed of plagioclase (NaAlSi3O8 – CaAl2Si2O8), pyroxene

(XY(Si, Al)2O6) (where X represents calcium, sodium, magnesium and more rarely zinc, and Y represents ions of smaller size, such as chromium or aluminum), and

2+ 2+ olivine ((Mg , Fe )2SiO4 ) as well as amounts of ilmenite (FeTiO3), magnetite

(Fe3O4), and hematite (Fe2O3). Table 2 shows the major elemental composition of

JSC-Mars-1A (Hooper et al, 1993).

Table 2: Chemical Composition of JSC-Mars-1A

Oxides JSC MARS-1A Wt.% SiO2 34.4* 43.5** Al2O3 18.5* 23.3* TiO2 3.0* 3.8* FeO3 12.4* 15.6** MnO 0.2* 0.3** CaO 4.9* 6.2** MgO 2.7* 3.4** K2O 0.5* 0.6** Na2O 1.9* 2.4** P2O5 0.7* 0.9** SO3 n.a* n.a** Cl n.a* n.a** LOI 21.8* n.a**

n.a.: not analyzed; all iron calculated as Fe2O3. LOI (loss on ignition) weight loss after 2 hrs.

900C°. * X-ray fluorescence, **X-ray fluorescence (volatile-free, normalized).

1.3- The Geological History of Earth and Mars.

Earth and Mars both have large, long lived sedimentary records with similarities as well as some discrepancies, (Figure 2). On Mars the igneous record mostly consists of basalts. In contrast, the upper portion of the continental lithosphere of the Earth is mostly composed of intensive granodiorite rocks that can be a dominant source for clastic and carbonate rocks. The sedimentary rocks that comprise the crust of Mars are older than the terrestrial deposits that comprise the upper crust of the Earth. A number of minerals that are dominant in the Martian sedimentary rocks have been identified at the surface of Mars by satellites and rovers/landers. The minerals identified are sulfates, carbonates, clays, and amorphous silica. The sedimentary rocks on the surface of Mars in comparison with the sedimentary rocks of Earth are richer in Fe and Mg, and poorer in Na and K. This might be due to the differences in crustal compositions or to the environments that formed these rocks. (Scott M. Mclennan, 2012)

Figure 2: Comparison of the geological timescales for Mars and Earth. (Scott M. Mclennan, 2012) 7

The upper portion of the continental crust of the earth is characterized by felsic, granitic rocks (Taylor Mclennan 1985). Hence, this crust is rich in silica

(SiO2), with elevated levels of incompatible elements (e.g. K, Th, U) and relatively low levels of ferromagnesian elements (e.g. Fe, Mg, Cr, and Ni). These elements are part of the minerals that form the igneous rocks such as quartz, plagioclase, K- feldspar and micas (Nesbitt and Young 1984). However, alkali and subalkaline basalts and their intrusive equivalents appear to dominate the Martian crust. Based on chemical mapping data, Martian crust has a mildly incompatible element-enriched basaltic composition (Taylor and McLennan 2009). Such a composition is likely to result in a mineralogy dominated by plagioclase, olivine, pyroxene, and Fe-Ti oxides,

(Table 3).

Table 3: Comparison of selected common sedimentary mineralogy observed on Earth with known mineralogy on Mars with idealized chemical formulas1

Earth Mars Sand-sized detritus Quartz SiO2 Plagioclase (Ca, Na) (Si, Al)4O4 K-feldspar KAlSiO8 Olivine (Fe, Mg)2SiO4 Plagioclase (Ca, Na) (Si, Al)4O8 Pyroxene XY (Si, Al)2O6 (Intermediate- Felsic Lithics) (Mafic Lithics)

Clays Kaolinite Al2Si2O5(OH)4 Kaolinite Al2Si2O5(OH)4 Illite K0.8Al2.8Si3.2O10(OH)2 - 2 2 Smectite e.g., Ca0.17(Al, Mg, Fe)2 Fe-Mg-smectite e.g., (Ca0.5, Na)0.3 (Si, Al)4O10(OH2) Fe2(Si, Al)4O10(OH)2.nH2O Sulfates Gypsum CaSO4.2H2O Gypsum CaSO4.2H2O Anhydrite CaSO4 Kieserite MgSO4.H2O 3 3+ Jarosite (Na, K, H3O) Fe 3 (SO4)6(OH)20(H2O) “Polyhydrated sulfates”4 Carbonates Aragonite CaCO3 Mg-carbonate MgCO3 Calcite CaCO3 Calcite CaCO3 Dolomite (Mg, Ca) CO3 Secondary iron oxide phases Hematite Fe2O3 Hematite Fe2O3 Goethite FeO.OH Goethite FeO.OH Nanophase iron oxides Secondary Silica phases Opal-A SiO2-nH2O Amorphous silica SiO2-nH2O Opal-CT SiO2-nH2O Micro-, mega-quartz SiO2 1 Idealized formula for Martian minerals are highly uncertain.2 Semctite compositions in terrestrial sediments are highly variable, and this is also likely the case for Mars. Formulas given here are examples.

1.4- Effects of Nutrient Supplements on the Mineralogical and Chemical Composition of JSC Mars 1A.

One of the future human missions on Mars will attempt to grow crops to provide sustainable food. Experimental results reported in the literature indicate that plants are able to grow on Martian regolith simulant JSC- MARS 1A without any addition of nutrients (Wamelink et al, 2014). All essential elements for the growth of plants are present in sufficient quantities in Martian soil, with the exception of

- + nitrogen. Nitrogen in reactive form (NO3 , NH4 ) is one of the essential elements necessary for almost all plant growth. The enormous source of available, reactive nitrogen compounds on Earth is due to the nitrogen fixing bacteria, which are absent on Mars. The absence of sufficient nitrogen may be solved by using nutrient solutions. Nutrient solutions were first created in the 19th century, and have been commonly used since to help plants grow. The nutrient solutions used to grow plants, called “water cultures”, had a simple composition and consisted of salts like KNO3,

Ca(NO3)2, KHPO4, MgSO4, and low concentrations of compounds containing iron.

Hoagland and Arnon (1950) developed the commonly used nutrient solution which contains major nutrients (N, P, S, K, Ca, Mg) and micro nutrients (Fe, Mn, Zn, B,

Cu, Mo) (Marschner, 1997) (Dally, 1974; States of Guernsey Horticultural Advisory

Service, 1974). The composition of the Hoagland’s solution is given in Appendix B.

2- Materials and Methodology

2.1- Materials

The tephra used in this study as Martian simulant regolith was mined from a cinder quarry on the slopes of the Pu’u Nene cone, Hawaii (Evans, D. L. and Adams,

J. B. 1997). In order to understand whether or not particle size might affect the chemical and mineralogical composition, all of the samples were sieved in order to separate them into different grain size fractions. Two samples of JSC Mars-1A regolith were purchased from Orbital Technologies Corporation in June 2016 (<5mm and <1mm) and sieved. The data on the <5mm sample grain size distribution is presented in (Table 4). The data on the <1mm sample is presented in Appendix A.

2.2- Analytical Methods

JSC Mars-1A size fractions were characterized by Powder X-ray diffraction

(PXRD), and scanning electron microscopy (SEM). Powder x-ray diffraction was used for the mineralogical characterization of crystalline materials, and scanning electron microscopy provided information about the sample’s surface topography and elemental composition.

Samples for PXRD analysis were placed on a quartz plate and inserted without any additional treatment. Each sample was at room temperature (25 C°). The

X-ray beam was produced by the generator at a voltage of 30.0kV. 11

In order to prepare SEM samples, Martian regolith simulant was mixed with epoxy mounted on a nylon nut and allowed to dry for 24 hours and polished by polishing machine. The operating temperature of the SEM was ~21 C°, the humidity 50%. The voltage with which the electrons are accelerated down the column was 15.0kV, and the vacuum in the specimen chamber was in the 10-5 to 10-6 Torr range.

Table 4: Grain Size Distribution of JSC Mars 1A <5mm Sample

Pore size of sieve Regolith(g) % 5.6 mm 0 0 4.75 mm 0.3538 1.22 4.00 mm 1.9231 6.63 2.80 mm 3.9911 13.76 2.00 mm 3.2975 11.37 1.40 mm 2.4688 8.51 1.00 mm 1.7450 6.01 710 µm 1.3878 4.78 500 µm 1.9045 6.56 355 µm 1.8003 6.20 250 µm 2.0254 6.98 180 µm 2.7131 9.35 125 µm 1.6887 5.82 90 µm 1.5877 5.47 75 µm 0.3732 1.28 63 µm 0.5296 1.82 < 63 µm 1.2031 4.14 Total= 28.9927g Total: 99.9%

We have performed analyses of five samples of JSC-MARS 1A. Four samples with different grain sizes (<5mm, <1mm, <125µm, <63µm) were analyzed.

Also, one sample of two different sizes (<5mm and <1mm) were mixed together and analyzed. The same mixture was used by a scientific team in the biology department of Florida Tech for a previous experiment in order to investigate the possibility of plant growth. In order to compare the chemical and mineralogical composition of this <5mm and <1mm regolith with the sample used in the biological department that promoted plant growth, PXRD and SEM analyses were performed.

The EVA program was used to determine the mineralogy of the samples from the X-ray diffraction patterns. The EVA program compared the sample PXRD patterns to those of standard minerals stored in a collection of databases (Table 5).

Table 5: Minerals that were included in the EVA software for possible detection by Powder X-ray Diffraction

No Mineral Name Formula 1 Albite NaAlSi3O8 2 Andesine (Na, Ca)AlSiO8 3 Anorthite CaAl2Si2O8 4 Augite (Ca, Na)(Mg, Fe, Al, Ti)(Si, Al)2O6 5 Alunite KAl3(SO4)2(OH)6 6 Anthophyllite Mg2Mg5Si8O2(OH)₂ 7 Anatase TiO2 2+ 3+ 8 Arfvedsonite [Na][Na2][(Fe )4Fe ][(OH)2|Si8O22] 2+ 9 Actinolite Ca2(Mg4.5-2.5Fe 0.5-2.5) Si8O22(OH)2 10 Biotite K(Mg, Fe)3AlSi3O10(F,OH)2 11 Bytownite (Ca, Na)[Al(Al, Si)Si2O8 12 Cristobalite SiO2

13 Coesite SiO2 14 Chamosit MgCaSi2O6 15 Chlorite (Fe, Mg, Al)6(Si, Al)4O10(OH)8 2+ 16 Clinochlore (Mg, Fe )5Al2Si3O10(OH)8 17 Diopside CaMgSi₂O₆ 18 Enstatite MgSiO3 19 Ferrihydrite 5Fe2O3 9H2O 20 Forsterite Mg2SiO4 3+ 2+ 3+ 21 Franklinfurnaceite Ca2Fe Mn 3Mn (Zn2Si2O10)(OH)8 23 Goethite FeO(OH) 24 Hematite Fe2O3 25 Hedenbergite CaFeSi2O6 26 Hornblende (Ca, Na)2(Mg, Fe, Al)5(Al, Si)8O22 (OH)2 27 ilmenite FeTiO 28 Jadeite NaAlSi2O6 3+ 29 Jarosite KFe 3(OH)6(SO4)2 30 Kaolinite Al2Si2O5(OH)4 31 Labradorite (Na, Ca)(Al, Si)4O8 32 Magnetite Fe3O4 33 Maghemite γ-Fe2O3 34 Oligoclase (Na, Ca)Al1-2Si3-2O8 2+ 2+ 35 Olivine (Mg , Fe )2SiO4 36 Pectolite NaCa2Si3O8(OH) 37 Pigeonite (Ca, Mg, Fe)(Mg, Fe)Si2O6 38 Pyroxene XY(Si, Al)2O6 39 Quartz SiO2 40 Rhodonite MnSiO₃ 41 Rutile TiO2 42 Sanidine K(AlSi3O8) 43 Spodumene LiAlSi₂O₆ 44 Stishovite SiO2 45 Siderite FeCO3 46 Tridymite SiO2 47 Tremolite Ca2(Mg, Fe)5Si8O22(OH)2 48 Wollastonite CaSiO3

To verify the identities of minerals, this study used at least three different standard databases. A numerical system (3, 2, 1, 0) was used to indicate the number of databases that positively identified each mineral. A value of 3, indicating all three databases positively identified a given mineral would signify a high level of confidence. Conversely, a valve of 0 indicates high confidence that this mineral is not present in the sample.

3- The Chemical Composition and Mineralogy of JSC MARS 1A after a Growth Experiment on Simulant.

We were able to analyze samples of JSC MARS 1A regolith which had been treated with Hoagland’s solution obtained from another research team from the astrobiology department at Florida Institute of Technology. This study was designed to investigate whether the nutrient supplement had affected the chemical composition and mineralogy of JSC-Mars 1A regolith before and after growing Lactuca sativa,

Solanum lycopersicum, Pisum sativum, and Capsicum annuum. The Hoagland’s supplement was added as a solution to the grain size mixture containing sizes <5mm and <1mm. PXRD and SEM results were recorded for the mixture before and after growing crops.

4- Results and Discussion.

4.1- Elemental Composition

Based on data from the two methods, PXRD and SEM, we were able to determine the chemical composition and mineralogy of the JSC-Mars1A samples of various grain sizes (Table 6 and 7). SEM analysis revealed that the major elements that made up the regolith simulant were Si, O, Al, Ca, Na, Ti and Fe. X-ray spectra and elemental maps were collected by SEM and are presented below Figure3 for the

<5mm and <63µm size fractions along with resulting quantitative analysis data. The data revealed a significant difference between percentage compositions of elements in each grain size. Figure 4 and Table 7 present the major elemental composition of

JSC-MARS 1A in two different grain sizes (<5mm and <63µm) which are discussed in Section 2.2. Note that the high percentage of carbon is due to the polymer that was used to encapsulate the samples for SEM analysis. Gold appears in some of the elemental data because it is used in the process of coating the samples prior to SEM analysis. Data on grain sizes <1mm and <125µm are presented in Appendix C.

Table 6: The number of databases that both positively and negatively identified each mineral

No Mineral DATA Formula 1 Albite 3 NaAlSi3O8 2 Andesine 2 (Na,Ca)AlSiO8 3 Anorthite 3 CaAl2SiO8 4 Augite 0 (Ca,Na)(Mg,Fe,Al, Ti)(Si,Al)2O6 5 Alunite 0 KAl3(SO4)2(OH)6 6 Anthophyllite 0 Mg2Mg5Si8O2(OH)₂, 7 Anatase 0 TiO2 2+ 3+ 8 Arfvedsonite 0 [Na][Na2][(Fe )4Fe ][(OH)2|Si8O22] 2+ 9 Actinolite 0 Ca2(Mg4.5-2.5Fe 0.5-2.5) Si8O22(OH)2 10 Biotite 0 K(Mg,Fe)3AlSi3O10(F,OH)2 11 Bytownite 2 (Ca,Na)[Al(Al,Si)Si2O8 12 Cristobalite 0 SiO2 13 Coesite 0 SiO2 14 Chamosit 0 MgCaSi2O6 15 Chlorite 0 (Fe, Mg, Al)6(Si, Al)4O10(OH)8 2+ 16 Clinochlor 0 (Mg, Fe )5Al2Si3O10(OH)8 17 Diopside 0 CaMgSi₂O₆ 18 Enstatite 0 MgSiO3 19 Ferrihydrite 0 5Fe2O3 9H2O 20 Forsterite 0 Mg2SiO4 3+ 2+ 3+ 21 Franklinfurnaceite 0 Ca2Fe Mn 3Mn (Zn2Si2O10)(OH)8 23 Goethite 0 FeO(OH) 24 Hematite 0 Fe2O3 25 Hedenbergite 0 CaFeSi2O6 26 Hornblende 0 (Ca,Na)2(Mg,Fe,Al)5(Al,Si)8O22 (OH)2 27 Ilmenite 0 FeTiO 28 Jadeite 0 NaAlSi2O6 3+ 29 Jarosite 0 KFe 3(OH)6(SO4)2 30 Kaolinite 0 Al2Si2O5(OH)4 31 Labradorite 3 (Na,Ca)1-₂Si3-2O₈ 32 Magnetite 0 Fe3O4 33 Maghemite 3 γ-Fe2O3 34 Oligoclase 3 (Na,Ca)Al1-2Si3-2O8

2+ 2+ 35 Olivine 0 (Mg , Fe )2SiO4 36 Pectolite 0 NaCa2Si3O8(OH) 37 Pigeonite 0 (Ca, Mg,Fe)(Mg,Fe)Si2O6 38 Pyroxene 0 XY(Si,Al)2O6 39 Quartz 0 SiO2 40 Rhodonite 0 MnSiO₃ 41 Rutile 0 TiO2 42 Sanidine 0 K(AlSi3O8) 43 Spodumene 0 LiAlSi2O₆ 44 Stishovite 0 SiO2 45 Siderite 0 FeCO3 46 Tridymite 0 SiO2 47 Tremolite 0 Ca2(Mg,Fe)5Si8O22(OH)2 48 Wollastonite 0 CaSiO3

Table 7: The elementary composition of the JSC Mars A1; <5mm and <63µm

Grain Size Element <5mm <63µm Wt.% At% Wt.% At% O 46.91 47.70 30.26 27.67 Na 00.51 00.36 00.09 00.06 Mg 00.20 00.14 00.10 00.06 Al 08.96 05.40 08.16 04.42 Si 06.96 04.03 05.11 02.66 Ca 00.33 00.13 02.18 00.80 Ti 00.48 00.16 00.48 00.15 Fe 01.70 00.50 01.06 00.28 C 30.37 41.13 52.40 63.84 P 00.27 00.14 00.10 00.05 Au 03.20 00.26 nd nd S 00.00 00.00 00.00 00.00 Cl 00.00 00.00 00.00 00.00 K 00.04 00.02 nd nd Mn 00.08 00.02 00.05 00.01

< 63µm <5mm

Figure 3: X-ray spectra collected by SEM for grain sizes <5mm and <63µm

<5mm <63µm

Figure 4: SEM images of the morphology of JSC MARS 1A

Images source: Scanning Electron Microscopy Lab, Biology Department, Florida Tech.

4.2- Correlation of Elemental data with Mineralogy.

The elements that we were able to associate with specific minerals are Al, Si,

Na, Ca and Fe. Other elements such as Mg and Ti were significant in some size fractions, however, it was not possible to associate them with specific minerals. In other words, Ti and Mg containing minerals weren’t found in PXRD analysis. For instance, the x-ray maps for grain sizes <5mm and <63µm (Figure 5 and Figure 6) indicate similar patterns of enrichment of the elements Al, Si, Na, and O suggesting the presence of albite which has the chemical formula NaAlSiO3 which was confirmed by PXRD analysis. Additionally, using the same SEM results there is evidence that anorthite is present; its chemical composition is CaAl2SiO8 and the elemental maps for Ca, Al, Si and oxygen can be seen to have similar patterns

(Figures 5 and 6). Along with albite and anorthite, other members of the oligoclase family were suggested by the SEM results as well. Lastly, even though there is not an abundance of iron (Figs.5 and 6), the PXRD analysis suggests the existence of maghemite within the sample.

Figure 5: Compositional image and x-ray mapping of the cross sections of JSC MARS 1A, grain size <5mm

Figure 6: Compositional image and x-ray mapping of the cross sections of JSC MARS 1A, grain size <63µm

All of the results from the PXRD analyses were evaluated and compared with data obtained from the American Mineralogist Crystal Structure Database: http://rruff.geo.arizona.edu/AMS/amcsd.php. Comparison of results with the databases were done through the EVA program. PXRD spectra of JSC Mars 1A are dominated by peaks corresponding to plagioclase series members, along with maghemite. While all grain size fractions contained the same minerals, fractions differed with respect to amounts of specific minerals. Figures 7-9 depict PXRD patterns for different grain sizes compared to the albite databases. For instance, a comparison of Figure 8 with Figure 9 reveals that albite is much more abundant in the grain size fraction <5mm than in the grain size fraction <63µm. This pattern is seen with other members of the plagioclase series. Additionally, a similar comparison of Figure 31 with Figure 34 reveals that maghemite is more abundant in the grain size <1mm than the grain size <125µm. In fact, all the minerals which were positively identified are more abundant in the grain sizes <5mm and <1mm than the grain sizes <125µm and <63µm (Figures 7-34).

Figure 7: The observed pattern for grain sizes (<1mm) versus the Albite database

Figure 8: The observed pattern for grain sizes (<5mm) versus the Albite database

Figure 9: The observed pattern for grain sizes (<63µm) versus the Albite database

Figure 10: The observed pattern for grain sizes (<125µm) versus the Albite database

Figure 11: The observed pattern for grain sizes (<1mm) versus the Andesine database

Figure 12: The observed pattern for grain sizes (<5mm) versus the Andesine database

Figure 13: The observed pattern for grain sizes (<63µm) versus the Andesine database

Figure 14: The observed pattern for grain sizes (<125µm) versus the Andesine database 26

Figure 15: The observed pattern for grain sizes (<1mm) versus the Anorthite database.

Figure 16: The observed pattern for grain sizes (<5mm) versus the Anorthite database

Figure 17: The observed pattern for grain sizes (<63µm) versus the Anorthite database

Figure 18. The observed pattern for grain sizes (<125µm) versus the Anorthite database.

Figure 19: The observed pattern for grain sizes (<1mm) versus the bytownite database.

Figure 20: The observed pattern for grain sizes (<5mm) versus the bytownite database

Figure 21: The observed pattern for grain sizes (<63µm) versus the bytownite database

Figure 22: The observed pattern for grain sizes (<125µm) versus the bytownite database

Figure 23: The observed pattern for grain sizes (<1mm) versus the labradorite database

Figure 24: The observed pattern for grain sizes (<5mm) versus the labradorite database 31

Figure 25: The observed pattern for grain sizes (<63µm) versus the labradorite database.

Figure 26: The observed pattern for grain sizes (<125µm) versus the labradorite database.

Figure 27: The observed pattern for grain sizes (<1mm) versus the oligoclase database

Figure 28: The observed pattern for grain sizes (<5mm) versus the oligoclase database 33

Figure 29: The observed pattern for grain sizes (<63µm) versus the oligoclase database

Figure 30: The observed pattern for grain sizes (<125µm) versus the oligoclase database.

Figure 31: The observed pattern for grain sizes (<1mm) versus the maghemite database

Figure 32: The observed pattern for grain sizes (<5mm) versus the maghemite database

Figure 33: The observed pattern for grain sizes (<63µm) versus the maghemite database

Figure 34: The observed pattern for grain sizes (<125µm) versus the maghemite database.

As discussed above, JSC MARS 1A is a volcanic ash mainly composed of plagioclase series members (The series ranges from albite to anorthite) and that includes the presence of albite, andesine, bytownite, labradorite, oligoclase and anorthite. Additionally, JSC MARS 1A was found to contain maghemite, (Table 8).

Table 8: Minerals identified in Mars regolith simulant.

No Mineral Name Database Composition 1 Albite 3 NaAlSi3O8 1 Andesine 2 (Na, Ca)AlSiO8 3 Anorthite 3 CaAl2Si2O8 4 Bytownite 2 (Ca,Na)[Al(Al,Si)]Si1O8 5 Labradorite 3 (Na,Ca)1-₂Si3-2O₈ 6 Maghemite 3 γ-Fe2O3 7 Oligoclase 3 (Na,Ca)Al1-1Si3-1O8

On the Earth, Feldspar minerals reflect specific environments and conditions during their formation (Deer et al., 1997). The composition of plagioclase minerals in metamorphic rocks can be an indicator of the grade of metamorphism of the mother rock. In contrast, the composition of plagioclases in igneous rocks reflects the chemical composition of magma that formed these minerals.

Plagioclase can be formed in felsic and mafic igneous rocks. Plagioclase minerals can vary consistently during crystallization processes from anorthite,

CaAl1Si1O8, to albite, NaAlSi3O8, (Table 9). Plagioclases can be chemically altered

37 to clay minerals such as halloysite, kaolinite, montmorillonite, and scapolite in the presence of water as well as in low-temperature conditions (e.g., Robertson and

Eggleton, 1991; Deer et al., 1997; Jeong, 1998; Arslan et al., 1006]). No evidence for the presence of clay minerals was found in this study.

Table 9: Composition of the plagioclase minerals.

Name Albite (Wt. %) Anorthite (Wt. %)

Albite 100-90 0-10

Oligoclase 90-70 10-30

Andesine 70-50 30-50

Labradorite 50-30 50-70

Anorthite 10-0 90-100

In addition, it should be noted that the PXRD spectra show no evidence of sulfates, carbonates, or kaolinite (a crystalline clay that requires water in order to form).

The composition of Martian soil mainly consists of approximately 44% silicon and 19% iron (Table1). Observational evidence suggests that iron is mainly present in its oxidized form. More importantly, the observational and simulation spectral evidence strongly suggests that the iron component of Martian soil is mostly present in poorly crystallized clusters of oxyhydroxy ferric iron, or as crystalline minerals having extremely small particle sizes ("nanophases" or "nanocrystals") (A.

Banin, AND L. Margulies 1993). 38

Most of the iron in the JSC Mars 1A was found as maghemite (훾-Fe2O3).

Maghemite can form through transformation of certain iron oxyhydroxide minerals, such as Lepidocrocite (훾 -FeOOH). To understand the mechanism of formation of nanophase iron, Banin et al. (1993) prepared clay containing nanophase particles of iron. The noncrystalline nature of the iron was verified through the extraction of iron with ammonium oxalate. Lepidocrocite (훾-FeOOH) is formed from a double iron

Fe(II)/Fe(III) hydroxy mineral. Magnetic measurements proved that Lepidocrocite

(훾-FeOOH) was converted to the stable maghemite (훾-Fe2O3) by moderate heat treatment and then to nanophase hematite (α-Fe2O3) by more vigorous heating

(Figure 35). Also, after mild heating, the iron-enriched clay became slightly magnetic, as was observed with Martian soil. This is strong evidence that the iron exists as nanophase iron oxides/oxyhydroxide in Martian soil. (A. Banin, and L.

Margulies 1993; Taylor and Schwertmann, 1978).

Figure 35: Structural and magnetic transformation of np iron oxide/oxyhydroxide deposited on clay.

Image source: (A. Banin, and L. Margulies, 1993) 39

On the basis of telescopic observations (1988 – 1990) along with laboratory studies, evidence led scientists to conclude that the iron oxides in Martian soil are noncrystalline or in the nanometer size range. This conclusion explains that the soil formation on Mars took place 3.5-4.0 b.y.a when Mars may have been warm and wet

(e.g., Banin et al., 1991; Gooding et al., 1991). Thus it appears that on Mars only a small portion of the iron oxides have crystallized and developed more thermodynamically stable mineralogical compositions. On Earth, similar iron oxides exist as transitionary phases which geologically become more stable minerals

(Grambow et al., 1985; Crovisier et al., 1987).

5 - Effects of Nutrient Supplements on the Mineralogical and Chemical Composition of JSC Mars 1A.

Even after adding nutrient supplements and growing crops in the JSC Mars

1A mixture (<1mm and <5mm), PXRD, SEM spectra, and X-ray elemental maps of the soil showed no significant changes in the chemical and mineral composition of the JSC Mars 1A, (Figures 36 and 37).

Figure 36: Compositional image and x-ray mapping of the cross sections of JSC MARS 1A Mixture (<1mm and <5mm)

Figure 37: Compositional image and x-ray mapping of the cross sections of JSC MARS 1A Mixture (<1mm and <5mm) after adding nutrient supplements and crop growth.

To understand the effects plant growth and nutrient supplements have on the soil, six samples (3 duplicates) were analyzed. Two sample of the <1mm and <5mm grain size mixture, two sample of the same mixture with Hoagland’s solution, and two sample of the mixture with supplements after plant growth. In order to ascertain the effect of positioning, 6 positions were tested by SEM for each sample to compare the composition of the samples more thoroughly and to increase confidence of comparing samples.

Tables 10 and 11 depict the concentration of each element in the six different positions in the JSC Mars 1A mixture (<5mm and <1mm) before and after the addition of nutrient supplements and growing crops. From these values a statistical comparison (t-test) was performed to observe any changes of chemical concentrations between the two samples. In this test, the P value, T state and T critical value of each element were calculated. t-test values did not indicate any statistically significant changes in elemental composition (wt. %) at a 95% confidence level due to adding nutrient solution or growing crops. The data on the t-test is presented in

Appendix F.

: Elemental Composition %) Elemental : (weight 10

of JSC Mars 1A mixture (<1mm and <5mm) and (<1mm mixture 1A JSC of Mars

Table Table

: Elemental Composition (weight %) %) Composition (weight Elemental :

11 Table Table

of JSC Mars 1A mixture (<1mm and <5mm) after growing crops after <5mm) growing and (<1mm mixture 1A JSC of Mars

6- Summary

JSC Mars 1A is a volcanic ash mainly composed of plagioclase. XRD peaks did not show evidence of sulfates, carbonates or clay minerals. The iron content of the

JSC Mars 1A regolith was found to be due to maghemite. The mineralogy of JSC

Mars 1A did not change with varying grain sizes with respect to the identity of minerals present but the quantitative analysis extracted from the spectral images reveal that there were quantitative differences between mineral abundances in each grain size. Figure 38 reveals the identification of all major PXRD peaks. In general, all minerals were found to be more abundant in the larger grain sizes compared to the smaller grain sizes. Similarly, SEM results did not reveal differences in elements present with grain size variation, but differences in elemental abundance were noted.

XRD and SEM results did not show any significant changes after adding the nutrient supplement and growing crops. JSC Mars 1A was not found to contain some of the minerals that have been found in Martian soil such as olivine or others previously identified by Morris, R. V. et al. (1993).

<63µm

<5mm

Figure 38: PXRD data for identified minerals in Mars regolith simulant

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APPENDIX A Table A-1. Mass data from sieving (grain size <1mm sample)

Pore size of sieve Regolith (g) %

710µm 1.9497 6.9

500 µm 3.9871 14.11

355 µm 3.7530 13.18

150 µm 4.1409 14.65

180 µm 6.4308 11.75

115 µm 1.8339 10.01

90 µm 1.8631 6.59

75 µm 0.5847 1.06

63 µm 0.9199 3.19

<63 µm 1.7819 6.30

Total= 18.1551 Total= 99.95

APPENDIX B Table B-1. Composition of the Hoagland’s solution (Macronutrients)

Macronutrients mg/L Ammonium Phosphate, Monobasic 115.0300 Calcium Chloride, Anhydrous 656.4000 Magnesium Sulfate, Anhydrous 140.7600 Potassium Chloride - Potassium Nitrate 606.6000 Potassium phosphate, Monobasic, - Anhydrous

Table B-1. Composition of the Hoagland’s solution (Micronutrients)

Micronutrients Mg/L

Boric Acid 1.8600

Copper II Chloride, Anhydrous 0.0600

Cupric Sulfate, Pentahydrate 0.0800

EDTA, Iron Sodium Salt -

Ferric Tartrate 5.3100

Manganese Chloride, Tetrahydrate 1.8100

Molybdenum Trioxide 0.0100

Zinc Chloride, Anhydrous -

Zinc Nitrate, Hexahydrate 0.1100

APPENDIX C SEM data on grain sizes <1mm and <115µm

SEM data on grain size <1mm Element Wt% At%

CK 18.61 39.88 OK 44.75 46.81 NaK 00.71 00.51 MgK 01.03 00.71 AlK 08.33 05.16 SiK 08.78 05.13 PK 00.15 00.08 AuM 03.71 00.31 SK 00.00 00.00 ClK 00.00 00.00 KK 00.06 00.01 CaK 00.57 00.14 TiK 00.71 00.15 MnK 00.04 00.01 FeK 01.51 00.76 Matrix Correction ZAF

Table C-1. Cumulative spectra and quantitative analysis for grain size <1mm

Figure C-1. SEM image of the morphology of JSC MARS 1A 53

SEM data on grain size <115µm

Element Wt% At% CK 49.46 61.88 OK 30.41 18.56 NaK 00.36 00.14 MgK 00.14 00.08 AlK 06.75 03.76 SiK 06.41 03.43 PK 00.11 00.10 SK 00.06 00.03 ClK 00.00 00.00 CaK 01.91 00.71 TiK 00.91 00.19 MnK 00.11 00.06 FeK 03.16 00.85 Matrix Correction ZAF

Table C-1. Cumulative spectra and quantitative analysis for grain size <115µm

Figure C-1. SEM image of the morphology of JSC MARS 1A

APPENDIX D Original XRD data for minerals identified in Mars regolith simulants.

1- Albite

2- Andesine

3- Anorthite

4- Bytownite

5- Maghemite

6- Labradorite

7- Olioclase.

APPENDIX E Tables F 1-8. T-test data for quantitative values of elements in JSC- Mars 1A mixture grain sizes (<5mm and <1mm) before and after growing crops

Table 1. T-test; Boron Table 1. T-test; Phosphor

Table 3. T-test; Potassium Table 4. T-test; Calcium

Table 5. T-test; Manganese Table 6. T-test; Iron

Table 7. T-test; Copper Table 8. T-test; Zinc