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NASA NTRS2003

Common Ion Effects In Zeoponic Substrates: Dissolution And Cation Exchange Variations Due to Additions of Calcite, Dolomite and Wollastonite

c1inoptilolite-rich tuff-hydroxyapatite mixture (zeoponic substrate) has the potential to serve as a synthetic soil-additive for plant growth. Essential plant macro-nutrients such as calcium, phosphorous, magnesium, ammonium and potassium are released into solution via dissolution of the hydroxyapatite and cation exchange on zeolite charged sites. Plant growth experiments resulting in low yield for wheat have been attributed to a Ca deficiency caused by a high degree of cation exchange by the zeolite. Batch-equilibration experiments were performed in order to determine if the Ca deficiency can be remedied by the addition of a second Ca-bearing, soluble, mineral such as calcite, dolomite or wollastonite. Variations in the amount of calcite, dolomite or wollastonite resulted in systematic changes in the concentrations of Ca and P. The addition of calcite, dolomite or wollastonite to the zeoponic substrate resulted in an exponential decrease in the phosphorous concentration in solution. The exponential rate of decay was greatest for calcite (5.60 wt. % -I), intermediate for wollastonite (2.85 wt.% -I) and least for dolomite (1.58 wt.% -I). Additions of the three minerals resulted in linear increases in the calcium concentration in solution. The rate of increase was greatest for calcite (3.64), intermediate for wollastonite (2.41) and least for dolomite (0.61). The observed changes in P and Ca concentration are consistent with the solubilities of calcite, dolomite and wollastonite and with changes expected from a common ion effect with Ca. Keywords: zeolite, zeoponics, common-ion effect, clinoptilolite, hydroxyapatite

Beiersdorfer, R. E.↗

NASA NTRS1995

Modeling transport kinetics in clinoptilolite-phosphate rock systems

Nutrient release in clinoptilolite-phosphate rock (Cp-PR) systems occurs through dissolution and cation-exchange reactions. Investigating the kinetics of these reactions expands our understanding of nutrient release processes. Research was conducted to model transport kinetics of nutrient release in Cp-PR systems. The objectives were to identify empirical models that best describe NH4, K, and P release and define diffusion-controlling processes. Materials included a Texas clinoptilolite (Cp) and North Carolina phosphate rock (PR). A continuous-flow thin-disk technique was used. Models evaluated included zero order, first order, second order, parabolic diffusion, simplified Elovich, Elovich, and power function. The power-function, Elovich, and parabolic-diffusion models adequately described NH4, K, and P release. The power-function model was preferred because of its simplicity. Models indicated nutrient release was diffusion controlled. Primary transport processes controlling nutrient release for the time span observed were probably the result of a combination of several interacting transport mechanisms.

NASA Center JSC↗

NASA NTRS1993

Solubility and cation exchange in phosphate rock and saturated clinoptilolite mixtures

Mixtures of zeolite and phosphate rock (PR) have the potential to provide slow-release fertilization of plants in synthetic soils by dissolution and ion-exchange reactions. This study was conducted to examine solubility and cation-exchange relationships in mixtures of PR and NH4- and K-saturated clinoptilolite (Cp). Batch-equilibration experiments were designed to investigate the effect of PR source, the proportion of exchangeable K and NH4, and the Cp to PR ratio on solution N, P, K, and Ca concentrations. The dissolution and cation-exchange reactions that occurred after mixing NH4- and K-saturated Cp with PR increased the solubility of the PR and simultaneously released NH4 and K into solution. The more reactive North Carolina (NC) PR rendered higher solution concentrations of NH4 and K when mixed with Cp than did Tennessee (TN) PR. Solution P concentrations for the Cp-NC PR mixture and the Cp-TN PR mixture were similar. Solution concentrations of N, P, K, and Ca and the ratios of these nutrients in solution varied predictably with the type of PR, the Cp/PR ratio, and the proportions of exchangeable K and NH4 on the Cp. Our research indicated that slow-release fertilization using Cp/PR media may provide adequate levels of N, P, and K to support plant growth. Solution Ca concentrations were lower than optimum for plant growth.

NASA Discipline Number 61-10↗

NASA NTRS1996

Dissolution kinetics of a lunar glass simulant at 25 degrees C: the effect of pH and organic acids

The dissolution kinetics of a simulated lunar glass were examined at pH 3, 5, and 7. Additionally, the pH 7 experiments were conducted in the presence of citric and oxalic acid at concentrations of 2 and 20 mM. The organic acids were buffered at pH 7 to examine the effect of each molecule in their dissociated form. At pH 3, 5, and 7, the dissolution of the synthetic lunar glass was observed to proceed via a two-stage process. The first stage involved the parabolic release of Ca, Mg, Al, and Fe, and the linear release of Si. Dissolution was incongruent, creating a leached layer rich in Si and Ti which was verified by transmission electron microscopy (TEM). During the second stage the release of Ca, Mg, Al, and Fe was linear. A coupled diffusion/surface dissolution model was proposed for dissolution of the simulated lunar glass at pH 3, 5, and 7. During the first stage the initial release of mobile cations (i.e., Ca, Mg, Al, Fe) was limited by diffusion through the surface leached layer of the glass (parabolic release), while Si release was controlled by the hydrolysis of the Si-O-Al bonds at the glass surface (linear release). As dissolution continued, the mobile cations diffused from greater depths within the glass surface. A steady-state was then reached where the diffusion rate across the increased path lengths equalled the Si release rate from the surface. In the presence of the organic acids, the dissolution of the synthetic lunar glass proceeded by a one stage process. The release of Ca, Mg, Al, and Fe followed a parabolic relationship, while the release of Si was linear. The relative reactivity of the organic acids used in the experiments was citrate > oxalate. A thinner leached layer rich in Si/Ti, as compared to the pH experiments, was observed using TEM. Rate data suggest that the chemisorption of the organic anion to the surface silanol groups was responsible for enhanced dissolution in the presence of the organic acids. It is proposed that the increased rate of Si release is responsible for the one stage parabolic release of mobile cations and the relatively thin leached layer compared to experiments at pH 3 and 5.

NASA Discipline Life Support Systems↗

NASA NTRS2022

Effect of Ni2+, Zn2+, and Co2+ on green rust transformation to magnetite

In this study, we investigated Ni2+, Zn2+, and Co2+ mineralogical incorporation and its effect on green rust transformation to magnetite. Mineral transformation experiments were conducted by heating green rust suspensions at 85 °C in the presence of Ni2+, Zn2+, or Co2+ under strict anoxic conditions. Transmission electron microscopy and powder X-ray diffraction showed the conversion of hexagonal green rust platelets to fine grained cubic magnetite crystals. The addition of Ni2+, Zn2+, and Co2+ resulted in faster rates of mineral transformation. The conversion of green rust to magnetite was concurrent to significant increases in metal uptake, demonstrating a strong affinity for metal sorption/ co-precipitation by magnetite. Dissolution ratio curves showed that Ni2+, Zn2+, and Co2+ cations were incorporated into the mineral structure during magnetite crystal growth. The results indicate that the transformation of green rust to magnetite is accelerated by metal impurities, and that magnetite is a highly effective scavenger of trace metals during mineral transformation. The implications for using diagenetic magnetite from green rust precursors as paleoproxies of Precambrian ocean chemistry are discussed.

Hydrosulfate green rust↗

NASA NTRSDate not supplied

Investigating Fifth Oxide Effect on CMXAS Glass Properties

Coatings for hot section aero turbine engine structural materials are subject to thermochemical degradation after interacting with calcium-magnesium-aluminosilicates (CMAS). Molten CMAS viscosity is the primary glass property of importance, correlating with coating infiltration and reaction depth. CMAS viscosity was measured using a spindle-dipped viscometer at temperatures between 1300-1550°C in 25°C increments. Experimental data were compared to Thermo-Calc and FactSage computational models, which showed good agreement with experimental trends. CMXAS compositions, where X denotes a fifth oxide, of Ca30.75-Mg9-X5-Al13-Si42.25 (single cation oxide mol%) for X = Fe2+, Fe3+, Gd3+, Hf4+, Na1+, Ti4+, Y3+, Yb3+, Zr4+ additions were used. Oxide precipitation was observed in X = Hf4+ , Zr4+ CMXAS specimens, indicating coating dissolution is an increased threat for T ≥ 1390°C. Molten CMAS and CMXAS viscosity measurements were shown to correlate with net cation field strength, offering an alternative in property prediction where thermodynamic data are unavailable.

Clark Avery Luckhardt↗

NASA NTRS2022

Abundant phosphorus expected for possible life in Enceladus’s ocean

Saturn’s moon Enceladus has a potentially habitable subsurface water ocean that contains canonical building blocks of life (organic and inorganic carbon, ammonia, possibly hydro-gen sulfide) and chemical energy (disequilibria for methanogenesis). However, its habit-ability could be strongly affected by the unknown availability of phosphorus (P). Here, we perform thermodynamic and kinetic modeling that simulates P geochemistry based on recent insights into the geochemistry of the ocean–seafloor system on Enceladus. We find that aqueous P should predominantly exist as orthophosphate (e.g., HPO422), and total dissolved inorganic P could reach 1027to 1022mol/kg H2O, generally increasing with lower pH and higher dissolved CO2, but also depending upon dissolved ammonia and silica. Levels are much higher than<10210mol/kg H2Ofrompreviousestimatesand close to or higher than∼1026mol/kg H2O in modern Earth seawater. The high P concentration is primarily ascribed to a high (bi)carbonate concentration, which decreases the concentrations of multivalent cations via carbonate mineral formation, allowing phosphate to accumulate. Kinetic modeling of phosphate mineral dissolution suggests that geologically rapid release of P from seafloor weathering of a chondritic rocky core could supply millimoles of total dissolved P per kilogram of H2Owithin105y, much less than the likely age of Enceladus’s ocean (108to 109y). These results provide further evidence of habitable ocean conditions and show that any oceanic life would not be inhibited by low P availability.

Enceladus ocean↗

NASA NTRS2018

Silica Dissolution and Precipitation in Galciated Volcanic Environments and Implications for Mars

The surface of Mars exhibits strong evidence for a widespread and long-lived cryosphere. Observations of the surface have identified phases produced by water-rock interactions, but the contribution of glaciers to the observed alteration mineralogy is unclear. To characterize the chemical alteration expected on an icy early Mars, we collected water and rock samples from terrestrial glaciated volcanics. We related geochemical measurements of meltwater to the mineralogy and chemistry of proglacial rock coatings. In these terrains, water is dominated by dissolved silica relative to other dissolved cations, particularly at mafic sites. Rock coatings associated with glacial striations on mafic boulders include a silica-rich component, indicating that silica precipitation is occurring in the subglacial environment. We propose that glacial alteration of volcanic bedrock is dominated by a combination of high rates of silica dissolution and precipitation of opaline silica. On Mars, cryosphere-driven chemical weathering could be the origin of observed silica-enriched phases.

Rutledge, A. M.↗

NASA NTRS2003

Solubility and Cation Exchange Properties of Synthetic Hydroxyapatite and Clinoptilolite Mixtures

A zeoponic plant growth system is defined as the cultivation of plants in artificial soils, which have zeolites as a major component. These systems: 1) can serve as a controllable and renewable fertilization system to provide plant growth nutrients; 2) can mitigate the adverse effects of contamination due to leaching of highly soluble and concentrated fertilizers; and 3) are being considered as substrates for plant growth in regenerative life-support systems for long-duration space missions. Batch-equilibrium studies of the dissolution and ion-exchange properties of mixtures of naturally-occurring Wyoming clinoptilolite (a zeolite) exchanged with K(+) or NH4(+); and synthetic hydroxyapatite were conducted to determine: 1) the plant availability of the macro-nutrients NH4-N, P, K, Ca, and Mg and 2) the effects of varying the clinoptilolite to hydroxyapatite ratio and the ratio of exchangeable cations (K(+) vs. NH4(+)) on clinoptilolite extraframework sites. The nutrients NH4-N (19.7 to 73.6 mg L(sup -1), P (0.57 to 14.99 mg L(sup- 1), K (14.8 to 104.9 mg L(sup -1), and Mg (0.11 to 6.68mg L(sup -1) are available to plants at sufficient levels. Solution Ca concentrations (0.47 to 3.40 mg L(sup -1) are less than optimal. Solution concentrations of NH4(+), K(+), Ca(2+), and Mg(2+) all decreased with increasing clinoptilolite to hydroxyapatite ratio in the sample. Solution concentrations of phosphorous initially increased, reached a maximum value and then decreased with increasing clinoptilolite to hydroxyapatite ratio in the sample. The NH4(+) -exchanged clinoptilolite is more efficient in dissolving synthetic hydroxyapatite than the K(+) -exchanged clinoptilolite. This suggests that NH4(+), which is less selective at clinoptilolite extraframework sites than K(+) is exchanged more readily by Ca(2+) and thereby enhances the dissolution of the synthetic hydroxyapatite.

Beiersdorfer, Raymond E.↗

NASA NTRS1990

Solid-support substrates for plant growth at a lunar base

Zeoponics is only in its developmental stages at the Johnson Space Center and is defined as the cultivation of plants in zeolite substrates that contain several essential plant growth cations on their exchange sites, and have minor amounts of mineral phases and/or anion-exchange resins that supply essential plant growth anions. Zeolites are hydrated aluminosilicates of alkali and alkaline earth cations with the ability to exchange most of their constituent exchange cations as well as hydrate/dehydrate without change to their structural framework. Because zeolites have extremely high cation exchange capabilities, they are very attractive media for plant growth. It is possible to partially or fully saturate plant-essential cations on zeolites. Zeoponic systems will probably have their greatest applications at planetary bases (e.g., lunar bases). Lunar raw materials will have to be located that are suited for the synthesis of zeolites and other exchange resings. Lunar 'soil' simulants have been or are being prepared for zeolite/smectite synthesis and 'soil' dissolution studies.

Ming, D. W.↗

NASA NTRS2001

Abiotic Versus Biotic Weathering Of Olivine As Possible Biosignatures

We are investigating the weathering of silicate minerals by both purely inorganic, and biologically mediated processes using field-emission scanning electron microscopy (FESEM) and energy dispersive x-ray spectroscopy (EDS). By resolving surface textures and chemical compositions of weathered surfaces at the sub-micron scale we hope to be able to distinguish abiotic from biotic weathering processes and so establish a new biosignature applicable to the study of astromaterials including but not limited to the Martian meteorites. Sterilized olivine grains (San Carlos, Arizona) no more than 1-2 mm in their longest dimension were optically assayed to be uniform in color and free of inclusions were selected as weathering subjects. Prior to all experiments surface morphologies and Fe/Mg ratios were determined for each grain using FE-SEM and EDS. Experiments were divided into two categories abiotic and biotic and were compared with "naturally" weathered samples. For the preliminary experiments, two trials (open and closed to the ambient laboratory environment) were performed under abiotic conditions, and three trials under biotic conditions (control, day 1 and day 2). The open system abiotic trials used sterile grains heated at 98 C and 200 C for both 24 and 48 hours in 1L double distilled de-ionized water. The closed system abiotic trials were conducted under the same conditions but in a sealed two layer steel/Teflon "bomb" apparatus. The biotic trials used sterile grains mounted in a flow-through device attached to a wellhead on the Columbia River aquifer. Several discolored, altered, grains were selected to document "natural" weathering surface textures for comparison with the experimental samples. Preliminary results indicate there are qualitative differences in weathered surface textures among all the designed experiments. The olivine grains in abiotic trials displayed etching, pitting, denticulate margins, dissolution and clay formation. The scale of the features ranged from tens to a few microns with textures that remained relatively sharp and were crystallographically controlled. These results were comparable to that observed in the "naturally" weathered comparison/reference grains. Chemical analysis by EDS indicates these textures correlated with the relative loss of Mg and Fe cations by diffusional processes. In contrast the biotic results indicated changes in the etching patterns on the scale of hundreds of nm, which are neither sharp nor crystallographically controlled (nanoetching). Organisms, organic debris and/or extracellular polymeric substances (biofilm) were often in close proximity or direct contact with the nanoetching. While there are many poorly constrained variables in natural weathering experiments to contend with, such as the time scale, the chemistry of the fluids and degree of biologic participation, some preliminary observations can be made: (1) certain distinct surface textures appear correlated with the specific processes giving rise to these textures; (2) the process of diffusing cations can produce many similar styles of surface textural changes; and (3) the main difference between abiotic and biotically produced weathering is the scale (microns versus nanometers) and the style (crystallographically versus noncrystallographically controlled) of the textural features. Further investigation into nanosize scale surface textures should attempt to quantify both textures and chemical changes of the role of microorganisms in the weathering of silicates. Additional experiments addressing nanoscale textures of shock features for comparison with the current data set.

Longazo, Teresa G.↗

NASA NTRS1999

Calcium Solubility and Cation Exchange Properties in Zeoponic Soil

An important aspect of a regenerative life support system at a Lunar or Martian outpost is the ability to produce food. Essential plant nutrients, as well as a solid support substrate, can be provided by: (1) treated Lunar or Martian regolith; (2) a synthetic soil or (3) some combination of both. A synthetic soil composed of ammonium- and potassium-saturated chinoptlolite (a zeolite mineral) and apatite, can provide slow-release fertilization of plants via dissolution and ion-exchange reactions. Previous equilibrium studies (Beiersdorfer, 1997) on mixtures of synthetic hydroxyapatite and saturated-clinoptilolite indicate that the concentrations of macro-nutrients such as ammonium, phosphorous, potassium, magnesium, and calcium are a function of the ratio of chinoptilolite to apatite in the sample and to the ratio of potassium to ammonium on the exchange sites in the clinoptilolite. Potassium, ammonium, phosphorous, and magnesium are available to plants at sufficient levels. However, calcium is deficient, due to the high degree of calcium adsorption by the clinoptilolite. Based on a series of batch-equilibration experiments, this calcium deficiency can be reduced by (1) treating the clinoptilolite with CaNO3 or (2) adding a second Ca-bearing mineral (calcite, dolomite or wollastonite) to the soil. Treating the Cp with CaNO3 results in increased Ca in solution, decreased P in solution and decreased NH4 in solution. Concentrations of K were not effected by the CaNO3 treatment. Additions of Cal, Dol and Wol changed the concentrations of Ca and P in solution in a systematic fashion. Cal has the greatest effect, Dol the least and Wol is intermediate. The changes are consistent with changes expected for a common ion effect with Ca. Higher concentrations of Ca in solution with added Cal, Dol or Wol do not result in changes in K or NH4 concentrations.

Beiersdorfer, Raymond E.↗

NASA NTRS2001

Plant Growth Experiments in Zeoponic Substrates: Applications for Advanced Life Support Systems

A zeoponic plant-growth system is defined as the cultivation of plants in artificial soils, which have zeolites as a major component (Allen and Ming, 1995). Zeolites are crystalline, hydrated aluminosilicate minerals that have the ability to exchange constituent cations without major change of the mineral structure. Recently, zeoponic systems developed at the National Aeronautics and Space Administration (NASA) slowly release some (Allen et at., 1995) or all of the essential plant-growth nutrients (Ming et at., 1995). These systems have NH4- and K-exchanged clinoptilolite (a natural zeolite) and either natural or synthetic apatite (a calcium phosphate mineral). For the natural apatite system, Ca and P were made available to the plant by the dissolution of apatite. Potassium and NH4-N were made available by ion-exchange reactions involving Ca(2+) from apatite dissolution and K(+) and NH4(+) on zeolitic exchange sites. In addition to NH4-N, K, Ca, and P, the synthetic apatite system also supplied Mg, S, and other micronutrients during dissolution (Figure 1). The overall objective of this research task is to develop zeoponic substrates wherein all plant growth nutrients are supplied by the plant growth medium for several growth seasons with only the addition of water. The substrate is being developed for plant growth in Advanced Life Support (ALS) testbeds (i.e., BioPLEX) and microgravity plant growth experiments. Zeoponic substrates have been used for plant growth experiments on two Space Shuttle flight experiments (STS-60; STS-63; Morrow et aI., 1995). These substrates may be ideally suited for plant growth experiments on the International Space Station and applications in ALS testbeds. However, there are several issues that need to be resolved before zeoponics will be the choice substrate for plant growth experiments in space. The objective of this paper is to provide an overview on recent research directed toward the refinement of zeoponic plant growth substrates.

Ming, Douglas W.↗

NASA NTRS1993

Characterization of Minnesota lunar simulant for plant growth

Processing of lunar regolith into a plant growth medium is crucial in the development of a regenerative life support system for a lunar base. Plants, which are the core of such a system, produce food and oxygen for humans and, at the same time, consume carbon dioxide. Because of the scarcity of lunar regolith, simulants must be used to infer its properties and to develop procedures for weathering and chemical analyses. The Minnesota Lunar Simulant (MLS) has been identified to date as the best available simulant for lunar regolith. Results of the dissolution studies reveal that appropriately fertilized MLS can be a suitable medium for plant growth. The techniques used in conducting these studies can be extended to investigate the suitability of actual lunar regolith as a plant growth medium. Dissolution experiments were conducted using the MLS to determine its nutritional and toxicity characteristics for plant growth and to develop weathering and chemical analysis techniques. Two weathering regimes, one with water and one with dilute organic acids simulating the root rhizosphere microenvironment, were investigated. Elemental concentrations were measured using inductively-coupled-plasma (ICP) emission spectrometry and ion chromatography (IC). The geochemical speciation model, MINTEQA2, was used to determine the major solution species and the minerals controlling them. Acidification was found to be a useful method for increasing cation concentrations to meaningful levels. Initial results indicate that MLS weathers to give neutral to slightly basic solutions which contain acceptable amounts of the essential elements required for plant nutrition (i.e., potassium, calcium, magnesium, sulfur, zinc, sodium, silicon, manganese, copper, chlorine, boron, molybdenum, and cobalt). Elements that need to be supplemented include carbon, nitrogen, and perhaps phosphorus and iron. Trace metals in solution were present at nontoxic levels.

Oglesby, James P.↗

NASA NTRSDate not supplied

Assessing Organic Preservation and the Implications for Potential Biosignatures in the Bastide Member of the Séítah Formation, Jezero Crater

Introduction: Olivine has the highest CO2 trapping potential of ultramafic minerals, due to its rapid rate of dissolution and high percentage of divalent cations/unpolymerized silicate tetrahedra [1]. It generates divalent carbonates from CO2 and sequesters CO2 into the mineral matrix of the target lithology. The co-occurrence of olivine and carbonate within abraded targets from the Bastide Member of the Séítah Formation (Fm) of the Jezero crater floor [2] suggests the carbonation of olivine occurred within the mineral matrix hosted in a subsurface system. Hydrothermal origins for the subsurface system are hypothesized from orbital data [3]. This is supported by the detection of hydration features within the rock as well as the carbonate features are solely detected within the abrasion patch but not the rock’s surface. Organic preservation potential of abrasion patches: We incorporated the SHERLOC/WATSON results acquired from the Dourbes, Garde, and Quartier abrasion patches in the Séítah Fm to investigate the organomineral associations, and determine the biosignature preservation potential of these rocks. Dourbes is dominated by olivine and has minor amounts of carbonate, hydrated Ca-sulfate, and amorphous or microcrystalline silicate. Fluorescence features (330-340 nm) are detected in discrete locales and could be consistent with double ring aromatic organic molecules; yet, these features do not appear to be associated with an identified mineral phase. Dark subhedral to euhedral olivine grains within the Garde abrasion patch often co-occur with carbonate-consistent spectral signatures in all analyzed scans. The availability of Fe2+ is a known influence on olivine dissolution rates [1] and SuperCam estimates of the olivine composition (Forsterite-60 average for Sols 202-234) may thereby provide a constraint on the carbonation extent. Carbonated olivine phenocrysts within the matrix may be due to aqueous alteration, as the carbonation of nodules is consistent with observations in other hydrothermal systems and within Martian meteorites (ALH84001) [4]. In comparison, the Quartier abrasion patch represents an extensively altered endmember within the Bastide Member of the Séítah Fm. It contains a fluorescence doublet at 305/325 nm that coexists with multiple species of Na-sulfate and Mg-sulfate, Mg-carbonates, olivine [5]. Aqueous alteration and implications for habitability: The identification of primary and secondary mineral phases observed in the Bastide Member suggests the release of cations from primary ultramafic minerals through aqueous alteration. Within Garde, the carbonate detected appears to be Mg-rich and likely formed from the in situ alteration of Mg-rich olivine within the region as carbonate has only been detected within the rock via in situ analysis. Carbonates derived from abiotic and biotic reactions preserve biosignatures (i.e. indices of habitability) on Earth. The detected carbonate phase found in association with fluorescent features within the rock matrix may also indicate potential organic compounds preserved in a putative hydrothermal system. Fluorescent features (~330 nm) are unique to Garde and Dourbes, though they are co-located to carbonate signatures solely within Garde, and between the light toned minerals. Identification of these fluorescent features may be consistent with 1-2 ring aromatic compounds. The limit of detection for Raman is multiple orders of magnitude greater than the limit of detection required for fluorescence [6]. Implications for provenance: Hydrothermal systems represent disequilibrium chemical conditions that are hypothesized to have supported the emergence of life and also preserve ancient carbon within precipitated carbonates [7]. Hydrothermal system associated carbonates are capable of preserving biosignatures up to an estimated ~3.77 – 4.28 Gya [8]. Thus, carbonated olivine found within the Séítah Fm may represent a high-potential biosignature preserving environment on Mars. The formation of carbonates by an aqueous alteration process, such as carbonation of olivine is also consistent with hypotheses for carbonate within the greater regional-olivine bearing unit [2,3], which contains Garde, Dourbes, and Quartier. Acknowledgments: This work was carried out at the Jet Propulsion Laboratory, The California Institute of Technology under a contract from NASA. References: [1] Wood et al., (2019) ES&T, 6, 10. [2] Stack, K. et al., (2020) Space Sci Rev, 216, 127. [3] Tarnas, J. et al., (2021) JGR: Planets, 126, 11. [4] Steele et al., (2007) Meteorit. Planet. Sci., 42, 9. [5] Murphy, A.E. et al., (2022) LPSC [6] Bhartia et al., (2021) Space Sci Rev, 217, 58. [7] Luther (2021) GRL, 48, e2021GL094869. [8] Dodd et al., (2017) Nature, 543, 60-64

E L Cardarelli↗

NASA NTRS2011

The Formation of Fe/Mg Smectite Under Mildly Acidic Conditions on Early Mars

The detection of Fe/Mg smectites and carbonate in Noachian and early Hesperian terrain of Mars has been used to suggest that neutral to mildly alkaline conditions prevailed during the early history of Mars. However, if early Mars was neutral to moderately alkaline with a denser CO2 atmosphere than today, then large carbonates deposits should be more widely detected in Noachian terrain. The critical question is: Why have so few carbonate deposits been detected compared to Fe/Mg smectites? We suggest that Fe/Mg smectites on early Mars formed under mildly acidic conditions, which would inhibit the extensive formation of carbonate deposits. The goal of this work is to evaluate the formation of Fe/Mg smectites under mildly acidic conditions. The stability of smectites under mildly acidic conditions is attributed to elevated Fe/Mg activities that inhibit smectite dissolution. Beidelite and saponite have been shown to form from hydrothermal alteration of basaltic glass at pH 3.5-4.0 in seawater solutions. Nontronite is also known to be stable in mildly acidic systems associated with mafic and ultramafic rock. Nontronite was shown to form in acid sulfate soils in the Bangkok Plain, Thailand due to oxidation of Fe-sulfides that transformed saponite to nontronite. Smectite is known to transform to kaolinite in naturally acid soils due to selective leaching of Mg. However, if Mg removal is limited, then based on equilibrium relationships, the dissolution of smectite should be minimized. If Fe and Mg solution activities are sufficiently high, such as might be found in a low water/rock ratio system that is poorly drained, smectite could form and remain stable under mildly acidic conditions on Mars. The sources of mild acidity on early Mars includes elevated atmospheric CO2 levels, Fe-hydrolysis reactions, and the presence of volcanic SO2 aerosols. Equilibrium calculations dictate that water equilibrated with an early Mars CO2 atmosphere at 1 to 4 bar yields a pH of 3.6 to 3.9. Fe hydrolysis reactions on Mars is another source of protons that would have contributed to acidity. The presence of SO2 from volcanic processes could also have contributed to geochemical acidification. These sources of acidity competed with base-forming cations that resulted in mildly acidic solutions that were not favorable for carbonate formation but may have allowed for Fe/Mg smectite formation. Noachian to early Hesperian Mars could have been mildly acidic, allowing Fe/Mg smectite formation but preventing widespread carbonate deposition. This paradigm shift from an early Mars that was neutral-alkaline to mildly acidic may possibly explain why there is a disparity between the occurrence of carbonate and Fe/Mg smectites. Potential microbiological activity would not be eliminated under a mildly acidic Mars; however, there could be tighter constraints as to the type and species of microbiology that could exist.

Sutter, Brad↗