ALBERT

Description: Aqueous alteration is the change in composition of a rock, produced in response to interactions with H2O-bearing ices, liquids, and vapors by chemical weathering. A variety of mineralogical and geochemical indicators for aqueous alteration on Mars have been identified by a combination of surface and orbital robotic missions, telescopic observations, characterization of Martian meteorites, and laboratory and terrestrial analog studies. Mineralogical indicators for aqueous alteration include goethite (lander), jarosite (lander), kieserite (orbiter), gypsum (orbiter) and other Fe-, Mg-, and Ca-sulfates (landers), halides (meteorites, lander), phyllosilicates (orbiter, meteorites), hematite and nanophase iron oxides (telescopic, orbiter, lander), and Fe-, Mg-, and Ca-carbonates (meteorites). Geochemical indicators (landers only) for aqueous alteration include Mg-, Ca-, and Fe-sulfates, halides, and secondary aluminosilicates such as smectite. Based upon these indicators, several styles of aqueous alteration have been suggested on Mars. Acid-sulfate weathering (e.g., formation of jarosite, gypsum, hematite, and goethite), may occur during (1) the oxidative weathering of ultramafic igneous rocks containing sulfides, (2) sulfuric acid weathering of basaltic materials, and (3) acid fog (i.e., vapors rich in H2SO4) weathering of basaltic or basaltic-derived materials. Near-neutral or alkaline alteration occurs when solutions with pH near or above 7 move through basaltic materials and form phases such as phyllosilicates and carbonates. Very low water:rock ratios appear to have been prominent at most of the sites visited by landed missions because there is very little alteration (leaching) of the original basaltic composition (i.e., the alteration is isochemical or in a closed hydrologic system). Most of the aqueous alteration appears to have occurred early in the history of the planet (3 to 4.5 billion years ago); however, minor aqueous alteration may be occurring at the surface even today (e.g., in thin films of water or by acid fog).

Description: Data collected by the Mars Phoenix Lander's Thermal and Evolved Gas Analyzer (TEGA) suggested the presence of calcium-rich carbonates as indicated by a high temperature CO2 release while a low temperature (approx.400-680 C) CO2 release suggested possible Mg- and/or Fe-carbonates [1,2]. Interpretations of the data collected by Mars remote instruments is done by comparing the mission data to a database on the thermal properties of well-characterized Martian analog materials collected under reduced and Earth ambient pressures [3,4]. We are proposing that "nano-phase" carbonates may also be contributing to the low temperature CO2 release. The objectives of this paper is to (1) characterize the thermal and evolved gas proper-ties of carbonates of varying particle size, (2) evaluate the CO2 releases from CO2 treated CaO samples and (3) examine the secondary CO2 release from reheated calcite of varying particle size.

Description: The Phoenix mission (PHX; May 25 - Nov. 2, 2008) studied the north polar region of Mars (68deg N) to understand the history of water and potential for habitability. Phoenix carried with it a wet chemistry lab (WCL) capable of determining the basic solution chemistry of the soil and the pH value, a thermal and evolved-gas analyzer capable of determining the mineralogy of the soil and detecting ice, microscopes capable of seeing soil particle shapes, sizes and colors at very high resolution, and a soil probe (TECP) capable of detecting unfrozen water in the soil. PHX coincided with an international effort to study the Earth s polar regions named the International Polar Year (IPY; 2007-2008). The best known Earth analog to the Martian high-northern plains, where Phoenix landed, are the McMurdo Dry Valleys (MDV), Antarctica (Fig. 1). Thus, the IPY afforded a unique opportunity to study the MDV with the same foci - history of water and habitability - as PHX. In austral summer 2007, our team took engineering models of WCL and TECP into the MDV and performed analgous measurements. We also collected sterile samples and analyzed them in our home laboratories using state-of-the-art tools. While PHX was not designed to perform biologic analyses, we were able to do so with the MDV analog samples collected.

Description: Carbonate occurs at the Comanche outcrops in Gusev Crater on the basis of analyses made by the Mars Exploration Rover Spirit [1]. Taken together, mineralogical data from Spirit's Moessbauer (MB) and Mini-TES spectrometer and chemical data from the APXS spectrometer show that Comanche carbonate has an Mg-Fe-rich bulk chemical composition, is present at high concentrations, and is distributed throughout the outcrop and not just at the MB and APXS analysis location. The granular outcrop texture and the observation that it appears to be resistant to weathering compared with surrounding material [1] imply that the carbonate may be present as a cement. A hydrothermal origin for the Comanche carbonate was inferred by analogy with laboratory experiments and with a carbonate occurrence within the Bockfjord volcanic complex on the island Spitsbergen (Svalbard, Norway) [1]. The laboratory carbonates, synthesized by precipitation from hydrothermal solutions, have (MB) parameters and average bulk chemical compositions that are characteristic of Comanche carbonate. The connection to Comanche carbonate is only through chemical data for certain occurrences of Spitsbergen carbonates. In fact, the common average bulk chemical composition for these Spitsbergen carbonates, the synthetic carbonates, the Comanche carbonate, and also the carbonate globules found in martian meteorite ALH84001 is a chemical constraint consistent with a hydrothermal formation process for all the carbonates [e.g., 1-3]. We develop here a link between MB data for the Comanche carbonate from MER and MB data for certain Spitsbergen carbonate occurrences from laboratory measurements. We also obtained visible and near- IR spectra on Spitsbergen carbonates for comparison with martian carbonate detections made on the basis of CRISM spectral data, e.g., in Nili Fossae [4].

Description: The Mars Phoenix Scout mission landed at the northernmost location (approx.68deg N) of any lander or rover on the martian surface. This paper compares the S mineralogy at the Phoenix landing site with S mineralogy of soils studied by previous Mars landers. S-bearing phases were not directly detected by the payload onboard the Phoenix spacecraft. Our objective is to derive the possible mineralogy of S-bearing phases at the Phoenix landing site based upon Phoenix measurements in combination with orbital measurements, terrestrial analog and Martian meteorite studies, and telescopic observations.

Description: 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.

Description: Phyllosilicates of the smectite group including Mg- and Fe-saponite and Fe(III)-rich nontronite have been identified on Mars. Smectites are believed to be formed under neutral to alkaline conditions that prevailed on early Mars. This hypothesis is supported by the observation of smectite and carbonate deposits in Noachian terrain on Mars. However, smectite may have formed under mildly acidic conditions. Abundant smectite formations have been detected as layered deposits hundreds of meters thick in intracrater depositional fans and plains sediments, while no large deposits of carbonates are found. Development of mildly acidic conditions at early Mars might allow formation of smectite but inhibit widespread carbonate precipitation. Little is known regarding the mechanisms of smectite formation from basaltic glass under acidic conditions. The objective of this study was to test a hypothesis that Mars-analogue basaltic glass alters to smectite minerals under acidic conditions (pH 4). The effects of Mg and Fe concentrations and temperature on smectite formation from basaltic glass were evaluated. Phyllosilicate synthesis was performed in batch reactors (Parr acid digestion vessel) under reducing hydrothermal conditions at 200 C and 100 C. Synthetic basaltic glass with a composition similar to that of the Gusev crater rock Adirondack (Ground surface APXS measurement) was used in these experiments. Basaltic glass was prepared by melting and quenching procedures. X-ray diffraction (XRD) analysis indicated that the synthesized glass was composed of olivine, magnetite and X-ray amorphous phase. Samples were prepared by mixing 250 mg Adirondack with 0.1 M acetic acid (final pH 4). In order to study influence of Mg concentration on smectite formation, experiments were performed with addition of 0, 1 and 10 mM MgCl2. After 1, 7 and 14 day incubations the solution composition was analyzed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and the altered glass and formed phyllosilicates were examined by XRD analysis. Mineralogical changes were significant in Adirondack incubated with 10 mM MgCl2 at pH 4 and heated at 200 C. X-ray diffraction analysis revealed formation of phyllosilicate during 14 day incubation (Figure 1). Smectite was confirmed as the phyllosilicate after treatments with glycerol and KCl and heating to 550 C. The position of 02l (4.60 A) and 060 (1.54 A) diffraction bands were indicative of trioctahedral smectite such as saponite. Analysis of solution composition demonstrated that aqueous concentration of Mg decreased from 10 mM to approx.4 mM after 7 day incubation likely due to saponite formation. Smectite also formed in Adirondack incubated with 0 mM MgCl2 at pH 4 and heated at 200 C. However, diffraction peak positions of 02l (4.52 A) and 060 (1.51 A) suggested formation of dioctahedral nontronite. The 100degC Mg and Fe(II) treated basaltic glass experiments are ongoing and results will be presented.

Description: This paper is a tribute to Dr Fred Munpton, the founder of the International Committee on Natural Zeolites (ICNZ), by one of his students, who later succeed him as president of the ICNZ. The tribute reflects on Dr. Mumpton's skills as an editor and his zeal for the study of natural zeolites.

Description: Perchlorate salts were discovered in the soils around the Phoenix landing site on the northern plains of Mars [1]. Perchlorate was detected by an ion selective electrode that is part of the MECA Wet Chemistry Laboratory (WCL). The discovery of a mass 32 fragment (likely 02) by the Thermal and Evolved-Gas Analyzer (TEGA) provided additional confirmation of a strong oxidizer in the soils around the landing site. The purpose of this paper is to evaluate the thermal and evolved gas behavior of perchlorate salts using TEGA-like laboratory testbed instruments. TEGA ovens were fabricated from high purity Ni. Hence, an additional objective of this paper is to determine the effects that Ni might have on the evolved gas behavior of perchlorate salts.