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DOE OSTI2020

Materials Data on MgSO4 by Materials Project

MgSO4 crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. Mg2+ is bonded to six O2- atoms to form MgO6 octahedra that share corners with six equivalent SO4 tetrahedra and edges with two equivalent MgO6 octahedra. There are a spread of Mg–O bond distances ranging from 2.00–2.30 Å. S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with six equivalent MgO6 octahedra. The corner-sharing octahedra tilt angles range from 43–53°. There are a spread of S–O bond distances ranging from 1.47–1.51 Å. There are three inequivalent O2- sites. In the first O2- site, O2- is bonded in a 3-coordinate geometry to two equivalent Mg2+ and one S6+ atom. In the second O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Mg2+ and one S6+ atom. In the third O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Mg2+ and one S6+ atom.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Materials Data on MgSO4 by Materials Project

MgSO4 crystallizes in the orthorhombic Cmcm space group. The structure is three-dimensional. Mg2+ is bonded to six O2- atoms to form MgO6 octahedra that share corners with six equivalent SO4 tetrahedra and edges with two equivalent MgO6 octahedra. There are two shorter (2.03 Å) and four longer (2.18 Å) Mg–O bond lengths. S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with six equivalent MgO6 octahedra. The corner-sharing octahedra tilt angles range from 44–53°. There is two shorter (1.47 Å) and two longer (1.51 Å) S–O bond length. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Mg2+ and one S6+ atom. In the second O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Mg2+ and one S6+ atom.

36 MATERIALS SCIENCE↗

NASA NTRS1978

Growth of fungi in NaCl-MgSO4 brines

Previous investigations have shown that common fungi of the Penicillium-Aspergillus group can be grown in a variety of brines or on moist salt crystals. This simulates salt flats as well as sizeable waterbodies stabilized as saturated brines such as Don Juan Pond (Antarctica), the Great Salt Lake of Utah, and the Dead Sea in the Jordan Valley. In general, salt media rich in KCl are favored over other alkali halides; the media become more selective as the salt concentration rises and nutrient requirements become more complex. In the present paper, it is shown that media which resemble the Dead Sea salt mix can, in fact, support the growth of selected fungal strains, even in the absence of reduced organic nutrients other than glucose. Such media may serve as models for localized microhabitats on Mars.

Siegel, S. M.↗

NASA NTRS2005

Stability of Magnesium Sulfate Minerals in Martian Environments

Viking Lander, Pathfinder, and Mars Exploration Rover missions to Mars have found abundant sulfur in surface soils and rocks, and the best indications are that magnesium sulfates are among the key hosts. At Meridiani Planum, MgSO4 salts constitute 15 to 40 wt.% of sedimentary rocks. Additional S is hosted by gypsum and jarosite. Reflectance and thermal emission spectroscopy is consistent with the presence of kieserite (MgSO4 H2O) and epsomite (MgSO4*7H2O). Theoretically, the dodecahydrate (MgSO4*12H2O) should also have precipitated. We first examine theoretically which MgSO4 minerals should have precipitated on Mars, and then how dehydration might have altered these minerals.

Marion, G. M.↗

NASA NTRS2002

Theoretical Study of Infrared and Raman Spectra of Hydrated Magnesium Sulfate Salts

Harmonic and anharmonic vibrational frequencies, as well as infrared and Raman intensities, are calculated for MgSO4.nH20 (n=1-3). Electronic structure theory at the second order Moller-Plesset perturbation theory (MP2) level with a triple-zeta + polarization (TZP) basis set is used to determine the geometry, properties, and vibrational spectra of pure and hydrated MgSO4 salts. The direct vibrational self-consistent field (VSCF) method and its correlation corrected (CC-VSCF) extension are used to determine anharmonic corrections to vibrational frequencies and intensities for the pure MgSO4 and its complex with one water molecule. Very significant differences are found between vibrational of water molecules in complexes with MgSO4 and pure water. Some of the O-H stretching frequencies are shifted to the red very significantly (by up to 1500-2000/cm) upon complexation with magnesium sulfate. They should be observed between 1700 and 3000/cm in a region very different from the corresponding O-H stretch frequency region of pure water (3700-3800/cm). In addition, the SO2 stretching vibrations are found at lower frequency regions than the water vibrations. They can serve as unique identifiers for the presence of sulfate salts. The predicted infrared and Raman spectra should be of valuable help in the design of future missions and analysis of observed data from the ice surface of Jupiter's moon Europa that possibly contains hydrated MgSO4 salts.

Chaban, Galina M.↗

NASA NTRS1991

The magnesium sulfate-water system at pressures to 4 kilobars

Hydrated magnesium sulfate constitutes up to 1/6 of the mass of carbonaceous chondrites, and probably is important in many icy asteroids and satellites. It occurs naturally in meteorites mostly as epsomite. MgSO4, considered anhydrously, comprises nearly 3/4 of the highly soluble fraction of C1 chondrites. Thus, MgSO4 is probably an important solute in cryovolcanic brines erupted on certain icy objects in the outer solar system. While the physiochemical properties of the water-magnesium sulfate system are well known at low pressures, planetological applications of these data are hindered by a dearth of useful published data at elevated pressures. Accordingly, solid-liquid phase equilibria was recently explored in this chemical system at pressures extending to about 4 kilobars. The water magnesium sulfate system in the region of the eutectic exhibits qualitatively constant behavior between pressures of 1 atm and 2 kbar. The eutectic melting curve closely follows that for water ice, with a freezing point depression of about 4 K at 1 atm decreasing to around 3.3 K at 2 kbars. The eutectic shifts from 17 pct. MgSO4 at 1 atm to about 15.3 pct at 2 kbars. Above 2 kbars, the eutectic melting curve again tends to follow ice.

Hogenboom, D. L.↗

NASA NTRS2002

Infrared Spectra of Hydrated Magnesium Salts and their Role in the Search for Possible Life Conditions on Jupiter Moons

Recent observations from the Galileo satellite indicate that three of the Jupiter moons, Europa, Ganymede, and Callisto, may have subsurface oceans. Possible existence of such ocean and the nature of its composition are of great interest to astrobiologists. Data from Galileo's NIMS spectrometer indicate the possibility of hydrated salts on Europa's surface. To aid in the design of future missions, we investigated infrared spectra of MgSO4-nH20, n=1-3 using ab initio calculations. Geometry, energetics, dipole moments, vibrational frequencies and infrared intensities of pure and hydrated MgSO4 salts were determined. Significant differences are found between vibrational spectra of water molecules in complexes with MgSO4 and pure water. Some of the O-H stretching frequencies in the complexes are shifted to the red by up to 1,500 - 2,000 per cm. In addition, the SO2 stretching vibrations are found at lower frequency regions than the water vibrations. The calculated bands of water and SO2 fragments can serve as markers for the existence of the salt-water complexes on the surface of Jupiter's moon.

Chaban, Galina↗

NASA NTRS1993

Phase equilibria of the magnesium sulfate-water system to 4 kbars

Magnesium sulfate is the most abundant salt in carbonaceous chondrites, and it may be important in the low-temperature igneous evolution and aqueous differentiation of icy satellites and large chondritic asteroids. Accordingly, we are investigating high-pressure phase equilibria in MgSO4-H2O solutions under pressures up to four kbars. An initial report was presented two years ago. This abstract summarizes our results to date including studies of solutions containing 15.3 percent, 17 percent, and 22 percent MgSO4. Briefly, these results demonstrate that increasing pressure causes the eutectic and peritectic compositions to shift to much lower concentrations of magnesium sulfate, and the existence of a new low-density phase of magnesium sulfate hydrate.

Hogenboom, D. L.↗

NASA NTRS1993

Crustal structure and igneous processes in a chondritic Io

Liquid sulfur can form when metal-free C1 or C2 chondrites are heated. It may be obtained either by direct melting of native sulfur in disequilibrated C1 or C2 chondrites or by incongruent melting of pyrite and other sulfides in thermodynamically equilibrated rocks of the same composition. Hence, Lewis considered C2 chondrites to be the best meteoritic analog for Io's bulk composition. Metal-bearing C3 and ordinary chondrites are too chemically reduced to yield liquid sulfur and are not thought to represent plausible analogs of Io's bulk composition. An important aspect of Lewis' work is that CaSO4 and MgSO4 are predicted to be important in Io. Real C1 and C2 chondrites contain averages of, respectively, 11 percent and 3 percent by mass of salts (plus water of hydration). The most abundant chondritic salts are magnesium and calcium sulfates, but other important components include sulfates of sodium, potassium, and nickel and carbonates of magnesium, calcium, and iron. It is widely accepted that chondritic salts are formed by low-temperature aqueous alteration. Even if Io originally did not contain salts, it is likely that aqueous alteration would have yielded several percent sulfates and carbonates. In any event, Io probably contains sulfates and carbonates. This report presents the results of a model of differentiation of a simplified C2 chondrite-like composition that includes 1.92 percent MgSO4, 0.56 percent CaSO4, 0.53 percent CaCO3, and 0.094 percent elemental sulfur. The temperature of the model is gradually increased; ensuing fractional melting results in these components extruding or intruding at gravitationally stable levels in Io's crust. Relevant phase equilibria were reviewed. A deficiency of high-pressure phase equilibria renders the present model qualitative.

Kargel, J. S.↗

NASA NTRS2004

Quantitative Mineralogical Analysis of Mars Analogues Using CHEMIN Data and Rietveld Refinement

Mineralogical analysis is a critical component of planetary surface exploration. Chemical data alone leave serious gaps in our understanding of the surfaces of planets where complex minerals may form in combination with H, S, and halogens. On such planets (e.g., Mars) a single chemical composition may represent a range of mineral assemblages. For example, Viking chemical analyses of excavated duricrust indicate that Mg and S are correlated and ~10% MgSO4 (anhydrous weight) is a likely cementing agent. Pathfinder chemical data support a similar abundance of MgSO4 in the most altered materials. However, there are many possible Mg-sulfates with widely varying hydration states (including dehydrated and 1-, 2-, 3-, 4-, 5-, 6-, and 7-hydrates). In addition, other sulfate minerals such as gypsum (CaSO4 .2H2O) and other salts containing Cl may also exist. X-ray diffraction (XRD) has the ability to decipher mixtures of these phases that would be difficult, if not impossible to unravel using only chemical or spectral data.

Bish, D. L.↗

DOE OSTI2024

Switchable Charge Storage Mechanism via in Situ Activation of MXene Enables High Capacitance and Stability in Aqueous Electrolytes

The need for reliable renewable energy storage devices has become increasingly important. However, the performance of current electrochemical energy storage devices is limited by either low energy or power densities and short lifespans. Herein, we report the synthesis and characterization of multilayer Ti 4 N 3 T x MXene in various aqueous electrolytes. We demonstrate that Ti 4 N 3 T x can be electrochemically activated through continuous cation intercalation over a 10 day period using cyclic voltammetry. A wide operating window of 2 V is maintained throughout activation. After activation, capacitance at 2 mV s -1 increases by 300%, 140%, and 500% in 1 M H2SO4, 1 M MgSO4, and 1 M KOH, respectively, while maintaining ~600 F g -1 at 2 mV s–1 after 50000 cycles in 1 M H 2 SO 4 . This activation process is possibly attributed to the unique morphology of the multilayered material, allowing cation intercalation to increase access to redox-active sites between layers. This work adds to the growing repository of electrochemically stable MXenes reported for aqueous energy storage applications. These findings offer a reliable option for reliable energy storage devices with potential applications in large-scale grid storage and electric vehicles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1974

Some characteristics of fructose 1,6-diphosphatase activity in rat liver

A reliable assay for hepatic fructose 1,6-diphosphatase in the rat was developed. It was found that the greatest enzymic activity and highest protein levels were eluted from the colored portion of the homogenate. When the substrate concentration was 0.01M, the enzyme had optimal activity when incubated with 0.01M MgSO4 for 10 min. at 37 C in 0.05M Tris-HC1 buffer, pH 7.5. Specificity for the substrate, fructose 1,6-diphosphate, was obtained at substrate concentration of 0.01M.

Ashman, P. U.↗

NASA NTRS1978

Near-opposition limb darkening of solids of planetary interest

Results are presented for a general laboratory study of the limb darkening at small phase angles of various materials of planetary interest, with particular attention given to the wavelength dependence of limb darkening. Only substances stable at room temperature were measured, including basalt, graphite, mixtures of MgO and charcoal powders, olivine, goethite, bronzite, CaCO3, MgSO4, BaSO4, limonite, and hematite. Previous studies aimed at determining the nature of limb darkening at opposition for different common materials are reviewed. It is found that the scattering properties of most particulate materials near phase zero can be described adequately by Minnaert's law, but that such a representation is totally inadequate for materials that tend to fracture into flakes with mirrorlike surfaces (e.g., bronzite and graphite). The results also indicate that materials such as olivine have scattering properties within deep absorption bands which exhibit definite departures from Minnaert's law at large angles of incidence or emission.

Veverka, J.↗

NASA NTRS1991

Brine volcanism and the interior structures of asteroids and icy satellites

Brine vulcanism, in which MgSO4 and Na2SO4 are shown by carbonaceous chondrite mineralogies and elemental abundances to be the most important solutes, is presently suggested to account for the resurfacing observed on such icy satellites as Europa and Ganymede, and to have been a significant factor in the evolution of chondritic asteroids. Hypersaline brines have lower viscosities than familiar silicate lavas, although they remain more viscous than pure water; aqueous sulfate flows are seen as capable of constructing the vast, low-relief volcanic plains observed on Ganymede and Europa.

Kargel, Jeffrey S.↗

NASA NTRS2000

Criteria for Remote Sensing Detection of Sulfate Cemented Soils on Mars

Spectral measurements of loose and cemented mixtures of palagonitic soil and sulfates were made to determine whether cemented soils could be identified on Mars. Cemented MgSO4 mixtures exhibit an enhanced 9 micron sulfate fundamental compared to gypsum mixtures due to more diffuse and pervasive cementing.

Cooper, Christopher D.↗

NASA NTRS2001

Sedimentary Geochemistry of Martian Samples from the Pathfinder Mission

The purpose of this research project was to evaluate the APXS data collected on soils and rocks at the Pathfinder site in terms of sedimentary geochemistry. Below are described the major findings of this research: (1) An influential model to explain the chemical variation among Pathfinder soils and rocks is a two component mixing model where rocks of fairly uniform composition mix with soil of uniform composition; (2) The very strong positive correlation between MgO and SO, points to a control by a MgSO4 mineral however, spectroscopic data continue to suggest that Fe-sulfates, notably schwertmannite and jarosite, may be important components; (3) In an attempt to better understand the causes of complexities in mixing relationships, the possible influence of sedimentary transport has been evaluated; (4) Another aspect of this research has been to examine the possibility of sedimentary silica being a significant phase on Mars; and (5) On Earth, the geochemistry of sedimentary rocks has been used to constrain the chemical composition of the continental crust and an important part of this research was to evaluate this approach for Mars.

McLennan, Scott M.↗

NASA NTRS2004

Lunar and Planetary Science XXXV: Mars Mineralogy: Weathered and Dry

The session "Mars Mineralogy: Weathered and Dry" presented the following reports:Hyperspectral and Field Mapping of an Archaean Komatiite Unit in the Pilbara Craton, Western Australia: Applications for CRISM Mission; Emission Spectroscopy of Smectites: Implications for the TES Andesite-weathered Basalt Debate; Volcanism and/or Aqueous Alteration on Mars: Constraints on Distinguishing Glass and Phyllosilicate in the Thermal Infrared; Olivine Weathering on Mars: Getting Back to Basics; Sulfate-cemented Soils Detected in TES Data Through the Application of an Automated Band Detection Algorithm; Thermal Emission Spectroscopy of Sulfates: Possible Hydrous Iron-Sulfate in the Soil at the MER-A Gusev Crater Landing Site ; Barite and Celestine Detection in the Thermal Infrared: Possible Application to Determination of Aqueous Environments on Mars; Search for Evaporite Minerals in Flaugergues Basin, Mars; Contributions from Hydrated States of MgSO4 to the Reservoir of Hydrogen at Equatorial Latitudes on Mars; Identification of a Quartz and Na-Feldspar Surface Mineralogy in Syrtis Major; Pigeonite Masquerading as Olivine at Mars: First Results from Mars Spectroscopy Consortium; Green Mars: Geologic Characteristics of Olivine-bearing Terrains as Observed by THEMIS, MOC, and MOLA; and Global Chemical Abundances and Distributions on Mars from MGS-TES Spectra.

Source record↗

NASA NTRS2008

Sulfur and Iron Speciation in Gas-rich Impact-melt Glasses from Basaltic Shergottites Determined by Microxanes

Sulfur is abundantly present as sulfate near Martian surface based on chemical and mineralogical investigations on soils and rocks in Viking, Pathfinder and MER missions. Jarosite is identified by Mossbauer studies on rocks at Meridian and Gusev, whereas MgSO4 is deduced from MgO - SO3 correlations in Pathfinder MER and Viking soils. Other sulfate minerals such as gypsum and alunogen/ S-rich aluminosilicates and halides are detected only in martian meteorites such as shergottites and nakhlites using SEM/FE-SEM and EMPA techniques. Because sulfur has the capacity to occur in multiple valence states, determination of sulfur speciation (sulfide/ sulfate) in secondary mineral assemblages in soils and rocks near Mars surface may help us understand whether the fluid-rock interactions occurred under oxidizing or reducing conditions. To understand the implications of these observations for the formation of the Gas-rich Impact-melt (GRIM) glasses, we determined the oxidation state of Fe in the GRIM glasses using Fe K micro-XANES techniques.

Sutton, S. R.↗