David L. Bish

Mineralogy of a Mudstone at Yellowknife Bay, Gale Crater, Mars

Sedimentary rocks at Yellowknife Bay (Gale crater) on Mars include mudstone sampled by the Curiosity rover. The samples, John Klein and Cumberland, contain detrital basaltic minerals, calcium sulfates, iron oxide or hydroxides, iron sulfides, amorphous material, and trioctahedral smectites. The John Klein smectite has basal spacing of ~10 angstroms, indicating little interlayer hydration. The Cumberland smectite has basal spacing at both ~13.2 and ~10 angstroms. The larger spacing suggests a partially chloritized interlayer or interlayer magnesium or calcium facilitating H2O retention. Basaltic minerals in the mudstone are similar to those in nearby eolian deposits. However, the mudstone has far less Fe-forsterite, possibly lost with formation of smectite plus magnetite. Late Noachian/Early Hesperian or younger age indicates that clay mineral formation on Mars extended beyond Noachian time.

BASELINE STUDIES OF THE CLAY MINERALS SOCIETY SOURCE CLAYS: POWDER X-RAY DIFFRACTION ANALYSES

The Clay Minerals Society maintains a repository of Source Clays to provide scientists and researchers with a readily available supply of consistent materials so that research conducted by different groups can be correlated to identical material. These Source Clays include kaolinite, smectite, chlorite, vermiculite, illite, palygorskite and other minerals. As most of the Source Clays are naturally occurring materials, they typically contain minor to significant amounts of other mineral impurities. When conducting research using these samples, it is important that their mineral content be well characterized. It is also often desirable to remove these impurities to produce pure clay samples. For example, when studying the biological effects of a particular clay mineral, it is imperative that all contaminants ( e.g. crystalline silica minerals) be removed from the clay in question so that experimental results can be attributed to the clay alone. If purification is required, the clays must be purified in a manner that does not significantly alter the physical or chemical properties of the samples. This chapter describes the X-ray diffraction (XRD) characteristics of a suite of Source Clays of The Clay Minerals Society and demonstrates methods of purification based on Stokes’ law of settling in suspension that can be used to purify the clays. We refer to samples obtained from P. Costanzo (see Costanzo, 2001) as ‘processed’ material and material obtained directly from the Source Clay Repository as ‘as-shipped’ material. Size fractionations and purifi-cations were performed on the ‘as-shipped’ material to obtain the highest purity possible and to identify the impurities that occur in the material. Powder XRD data were collected for the Source Clays on a Siemens D500 powder X-ray diffractometer using CuKα radiation, incident- and diffracted-beam Soller slits, and a Kevex solid-state Si(Li) detector. Data were collected from 2 to 70°2𝛉 using a step size of 0.02°2𝛉 …

Rietveld refinement of the kaolinite structure at 1.5 K

The crystal structure of Keokuk kaolinite, including all H atoms, was refined in space group C1 using low-temperature (1.5 K) neutron powder diffraction data (λ = 1.9102 Å) and Rietveld refinement/difference-Fourier methods to Rwp = 1.78%, reduced χ2 = 3.32. Unit-cell parameters are: a = 5.1535(3) Å, b = 8.9419(5) Å, c = 7.3906(4) Å, α = 91.926(2)°, β = 105.046(2)°, γ = 89.797(2)°, and V = 328.70(5) Å3. Unit-cell parameters show that most of the thermal contraction occurred along the [001] direction, apparently due to a decrease in the interlayer distance. The non-H structure is very similar to published C1 structures, considering the low temperature of data collection, but the H atom positions are distinct. The inner OH group is essentially in the plane of the layers, and the inner-surface OH groups make angles of 60°–73° with the (001) plane. Difference-Fourier maps show minor anisotropy of the inner-OH group in the [001] direction, but the inner-surface OH groups appear to have their largest vibrational (or positional disorder) component parallel to the layers. Although no data indicate a split position of any of the H sites in kaolinite, there is support for limited random positional disorder of the H atoms. However, these data provided no support for a space group symmetry lower than C1.

Curiosity at Gale Crater, Mars: Characterization and Analysis of the Rocknest Sand Shadow

The Rocknest aeolian deposit is similar to aeolian features analyzed by the Mars Exploration Rovers (MERs) Spirit and Opportunity. The fraction of sand <150 micrometers in size contains ~55% crystalline material consistent with a basaltic heritage and ~45% x-ray amorphous material. The amorphous component of Rocknest is iron-rich and silicon-poor and is the host of the volatiles (water, oxygen, sulfur dioxide, carbon dioxide, and chlorine) detected by the Sample Analysis at Mars instrument and of the fine-grained nanophase oxide component first described from basaltic soils analyzed by MERs. The similarity between soils and aeolian materials analyzed at Gusev Crater, Meridiani Planum, and Gale Crater implies locally sourced, globally similar basaltic materials or globally and regionally sourced basaltic components deposited locally at all three locations.

X-ray diffraction results from mars science laboratory: Mineralogy of rocknest at Gale crater

The Mars Science Laboratory rover Curiosity scooped samples of soil from the Rocknest aeolian bedform in Gale crater. Analysis of the soil with the Chemistry and Mineralogy (CheMin) x-ray diffraction (XRD) instrument revealed plagioclase (~An57), forsteritic olivine (~Fo62), augite, and pigeonite, with minor K-feldspar, magnetite, quartz, anhydrite, hematite, and ilmenite. The minor phases are present at, or near, detection limits. The soil also contains 27 ± 14 weight percent x-ray amorphous material, likely containing multiple Fe3+- and volatile-bearing phases, including possibly a substance resembling hisingerite. The crystalline component is similar to the normative mineralogy of certain basaltic rocks from Gusev crater on Mars and of martian basaltic meteorites. The amorphous component is similar to that found on Earth in places such as soils on the Mauna Kea volcano, Hawaii.

Magnesium sulphate salts and the history of water on Mars

Recent reports of ∼30 wt% of sulphate within saline sediments on Mars—probably occurring in hydrated form—suggest a role for sulphates in accounting for equatorial H2O observed in a global survey by the Odyssey spacecraft. Among salt hydrates likely to be present, those of the MgSO4·nH2O series have many hydration states. Here we report the exposure of several of these phases to varied temperature, pressure and humidity to constrain their possible H2O contents under martian surface conditions. We found that crystalline structure and H2O content are dependent on temperature–pressure history, that an amorphous hydrated phase with slow dehydration kinetics forms at <1% relative humidity, and that equilibrium calculations may not reflect the true H2O-bearing potential of martian soils. Mg sulphate salts can retain sufficient H2O to explain a portion of the Odyssey observations. Because phases in the MgSO4·nH2O system are sensitive to temperature and humidity, they can reveal much about the history of water on Mars. However, their ease of transformation implies that salt hydrates collected on Mars will not be returned to Earth unmodified, and that accurate in situ analysis is imperative.

Soil Diversity and Hydration as Observed by ChemCam at Gale Crater, Mars

The ChemCam instrument, which provides insight into martian soil chemistry at the submillimeter scale, identified two principal soil types along the Curiosity rover traverse: a fine-grained mafic type and a locally derived, coarse-grained felsic type. The mafic soil component is representative of widespread martian soils and is similar in composition to the martian dust. It possesses a ubiquitous hydrogen signature in ChemCam spectra, corresponding to the hydration of the amorphous phases found in the soil by the CheMin instrument. This hydration likely accounts for an important fraction of the global hydration of the surface seen by previous orbital measurements. ChemCam analyses did not reveal any significant exchange of water vapor between the regolith and the atmosphere. These observations provide constraints on the nature of the amorphous phases and their hydration.

FULLPAT: a full-pattern quantitative analysis program for X-ray powder diffraction using measured and calculated patterns

FULLPAT is a quantitative X-ray diffraction methodology that merges the advantages of existing full-pattern fitting methods with the traditional reference intensity ratio (RIR) method. Like the Rietveld quantitative analysis method, it uses complete diffraction patterns, including the background. However, FULLPAT can explicitly analyze all phases in a sample, including partially ordered or amorphous phases such as glasses, clay minerals, or polymers. Addition of an internal standard to both library standards and unknown samples eliminates instrumental and matrix effects and allows unconstrained analyses to be conducted by direct fitting of library standard patterns to each phase in the sample. Standard patterns may include data for any solid material including glasses, and calculated patterns may also be used. A combination of standard patterns is fitted to observed patterns using least-squares minimization, thereby reducing user intervention and bias. FULLPAT has been coded into Microsoft EXCEL using standard spreadsheet functions.

Stability of hydrous minerals on the martian surface

The presence of water-bearing minerals on Mars has long been discussed, but little or no data exist showing that minerals such as smectites and zeolites may be present on the surface in a hydrated state (i.e., that they could contain H 2O molecules in their interlayer or extraframework sites, respectively). We have analyzed experimental thermodynamic and X-ray powder diffraction data for smectite and the most common terrestrial zeolite, clinoptilolite, to evaluate the state of hydration of these minerals under martian surface conditions. Thermodynamic data for clinoptilolite show that water molecules in its extra-framework sites are held very strongly, with enthalpies of dehydration for Ca-clinoptilolite up to three times greater than that for liquid water. Using these data, we calculated the Gibbs free energy of hydration of clinoptilolite and smectite as a function of temperature and pressure. The calculations demonstrate that these minerals would indeed be hydrated under the very low-P (H2O) conditions existing on Mars, a reflection of their high affinities for H 2O. These calculations assuming the partial pressure of H2O and the temperature range expected on Mars suggest that, if present on the surface, zeolites and Ca-smectites could also play a role in affecting the diurnal variations in martian atmospheric H 2O because their calculated water contents vary considerably over daily martian temperature ranges. The open crystal structure of clinoptilolite and existing hydration and kinetic data suggest that hydration/dehydration are not kinetically limited. Based on these calculations, it is possible that hydrated zeolites and clay minerals may explain some of the recent observations of significant amounts of hydrogen not attributable to water ice at martian mid-latitudes.

Sources and sinks of clay minerals on Mars

The recent identification of clay minerals on the Martian surface using visible–near infrared reflectance spectroscopy has had a profound effect on our view of aqueous alteration on Mars. Smectite, chlorite, kaolin group, and serpentine group minerals have been detected using the CRISM and OMEGA spectrometers, with Fe/Mg-smectite and chlorite varieties being the dominant types discovered throughout the ancient crust. Aqueous, eolian, and impact processes have transported and recycled some of these clays such that their current locations may not accurately reflect their formation environments. However, detrital clays could prove useful for constraining transport pathways and sediment provenance. Here we discuss the impact craters and channels that comprise the Uzboi–Ladon–Morava system, including Holden, Eberswalde, and Ladon craters, which represents a large-scale sediment sink for clay minerals derived from the surrounding Noachian crust. This system contains thick deposits of clay mineral-bearing strata that likely record a wide range of alluvial, fluvial, lacustrine, and eolian processes that provide direct insight into the Martian clay cycle. Broad concepts of sediment sources, sinks, and sediment transport paths can be outlined using orbital data, but future in situ exploration of the Martian sedimentary rock record will be necessary to distinguish fully between detrital and authigenic clay minerals, and thus to determine environmental conditions and transitions on ancient Mars.