E. C. Sklute

Low temperature aqueous alteration of basalt: Mineral assemblages of Deccan basalts and implications for Mars

Spectra of basalt samples were dominated by Fe 2+ crystal field transitions with weak alteration bands near 1.4 and/or 1.9 mm. Reststrahlen bands in mid-infrared showed the convolution of plagioclase and pyroxene features typical of basalts. Saprolite samples were incompletely leached, and their spectra were dominated by complex Al- and Fe/Mg-bearing smectite clays and retained no original mafic signatures. XRD and Mossbauer detected pyroxene and plagioclase not visible by reflectance spectroscopy in some saprolite samples. Zeolites were present throughout the saprolite. The laterite was the most leached horizon, and all analyses showed kaolinite and iron oxide assemblages. This kaolinite and hematite association would be expected if kaolinite on Mars formed through leaching under conditions similar to those on Earth and has implications for abundant freshwater on the Martian surface.

Morphological, structural, and spectral characteristics of amorphous iron sulfates

Current or past brine hydrologic activity on Mars may provide suitable conditions for the formation of amorphous ferric sulfates. Once formed, these phases would likely be stable under current Martian conditions, particularly at low- to mid-latitudes. Therefore, we consider amorphous iron sulfates (AIS) as possible components of Martian surface materials. Laboratory AIS were created through multiple synthesis routes and characterized with total X-ray scattering, thermogravimetric analysis, scanning electron microscopy, visible/near-infrared (VNIR), thermal infrared (TIR), and Mössbauer techniques. We synthesized amorphous ferric sulfates (Fe(III)2(SO4)3 · ~ 6-8H2O) from sulfate-saturated fluids via vacuum dehydration or exposure to low relative humidity (<11%). Amorphous ferrous sulfate (Fe(II)SO4 · ~1H2O) was synthesized via vacuum dehydration of melanterite. All AIS lack structural order beyond 11 Å. The short-range (<5 Å) structural characteristics of amorphous ferric sulfates resemble all crystalline reference compounds; structural characteristics for the amorphous ferrous sulfate are similar to but distinct from both rozenite and szomolnokite. VNIR and TIR spectral data for all AIS display broad, muted features consistent with structural disorder and are spectrally distinct from all crystalline sulfates considered for comparison. Mössbauer spectra are also distinct from crystalline phase spectra available for comparison. AIS should be distinguishable from crystalline sulfates based on the position of their Fe-related absorptions in the visible range and their spectral characteristics in the TIR. In the NIR, bands associated with hydration at ~1.4 and 1.9 μm are significantly broadened, which greatly reduces their detectability in soil mixtures. AIS may contribute to the amorphous fraction of soils measured by the Curiosity rover.

Structural and spectroscopic changes to natural nontronite induced by experimental impacts between 10 and 40 GPa

Many phyllosilicate deposits remotely detected on Mars occur within bombarded terrains. Shock metamorphism from meteor impacts alters mineral structures, producing changed mineral spectra. Thus, impacts have likely affected the spectra of remotely sensed Martian phyllosilicates. We present spectral analysis results for a natural nontronite sample before and after laboratory-generated impacts over five peak pressures between 10 and 40 GPa. We conducted a suite of spectroscopic analyses to characterize the samples impact-induced structural and spectral changes. Nontronite becomes increasingly disordered with increasing peak impact pressure. Every infrared spectroscopic technique used showed evidence of structural changes at shock pressures above ~25 GPa. Reflectance spectroscopy in the visible near-infrared region is primarily sensitive to the vibrations of metal–OH and interlayer H2O groups in the nontronite octahedral sheet. Midinfrared (MIR) spectroscopic techniques are sensitive to the vibrations of silicon and oxygen in the nontronite tetrahedral sheet. Because the tetrahedral and octahedral sheets of nontronite deform differently, impact-driven structural deformation may contribute to differences in phyllosilicate detection between remote sensing techniques sensitive to different parts of the nontronite structure. Observed spectroscopic changes also indicated that the samples octahedral and tetrahedral sheets were structurally deformed but not completely dehydroxylated. This finding is an important distinction from previous studies of thermally altered phyllosilicates in which dehydroxylation follows dehydration in a stepwise progression preceding structural deformation. Impact alteration may thus complicate mineral-specific identifications based on the location of OH-group bands in remotely detected spectra. This is a key implication for Martian remote sensing arising from our results.

Optical constants of synthetic potassium, sodium, and hydronium jarosite

Abstract The hydroxy sulfate jarosite [(K,Na,H3O)Fe3(SO4)2(OH)6] has both been discovered on Mars, and is associated with areas of highly acidic runoff on Earth. Because jarosite is extremely sensitive to formation conditions, it is an important target mineral for remote sensing applications. Yet at visible and near infrared (VNIR) wavelengths, where many spacecraft spectrometers collect data, the spectral abundance of a mineral in a mixture is not linearly correlated with the surface abundance of that mineral. Radiative transfer modeling can be used to extract quantitative abundance estimates if the optical constants (the real and imaginary indices of refraction, n and k) for all minerals in the mixture are known. Unfortunately, optical constants for a wide variety of minerals, including sulfates like jarosite, are not available. This is due, in part, to the inherent difficulty in obtaining such data for minerals that tend to crystallize naturally as fine-grained (~10 μm) powders, like many sulfates including jarosite. However, the optical constants of powders can be obtained by inverting the equation of radiative transfer and using it to model laboratory spectra. In this paper, we provide robust n and k data for synthetic potassium, hydronium, and sodium jarosite in the VNIR. We also explicitly describe the calculation procedures (including access to our Matlab code) so that others may obtain optical constants of additional minerals. Expansion of the optical constants library in the VNIR will facilitate the extraction of quantitative mineral abundances, leading to more in-depth evaluations of remote sensing target locations.

Determination of VNIR optical constants of synthetic postassium jarosite using the hapke treatment of r adiative transfer theory

Visible and near infrared optical constants are required to quantitatively determining mineral abundances from remote sensing data. Preliminary optical constants of a synthetic potassium jarosite, an important sulfate mineral on both Earth and Mars, are determined using a new MatLab encoded minimization routine based on Hapkes treatment of radiative transfer theory. The steps for determining these optical constants are delineated theoretically and programmatically in an attempt to assist the expansion of the library of optical data.