Joseph R. Michalski

Spectroscopic study of the dehydration and/or dehydroxylation of phyllosilicate and zeolite minerals

[1]xa0Phyllosilicates on Mars mapped by infrared spectroscopic techniques could have been affected by dehydration and/or dehydroxylation associated with chemical weathering in hyperarid conditions, volcanism or shock heating associated with meteor impact. The effects of heat-induced dehydration and/or dehydroxylation on the infrared spectra of 14 phyllosilicates from four structural groups (kaolinite, smectite, sepiolite-palygorskite, and chlorite) and two natural zeolites are reported here. Pressed powders of size-separated phyllosilicate and natural zeolite samples were heated incrementally from 100°C to 900°C, cooled to room temperature, and measured using multiple spectroscopic techniques: midinfrared (400–4000 cm−1) attenuated total reflectance, midinfrared reflectance (400–1400 cm−1), and far-infrared reflectance (50–600 cm−1) spectroscopies. Correlated thermogravimetric analysis and X-ray diffraction data were also acquired in order to clarify the thermal transformation of each sample. For phyllosilicate samples, the OH stretching (∼3600 cm−1), OH bending (∼590–950 cm−1), and/or H2O bending (∼1630 cm−1) bands all become very weak or completely disappear upon heating to temperatures > 500°C. The spectral changes associated with SiO4 vibrations (∼1000 cm−1 and ∼500 cm−1) show large variations depending on the compositions and structures of phyllosilicates. The thermal behavior of phyllosilicate IR spectra is also affected by the type of octahedral cations. For example, spectral features of Al3+-rich smectites are more stable than those of Fe3+-rich smectites. The high-temperature (>800°C) spectral changes of trioctahedral Mg2+-rich phyllosilicates such as hectorite, saponite, and sepiolite result primarily from crystallization of enstatite. Phyllosilicates with moderate Mg2+ concentration (e.g., palygorskite, clinochlore) and dioctahedral montmorillonites (e.g., SAz-1 and SCa-3) with partial Mg2+-for-Al3+ substitution all have new spectral feature developed at ∼900 cm−1 upon heating to 800°C. Compared with phyllosilicates, spectral features of two natural zeolites, clinoptilolite and mordenite, are less affected by thermal treatments. Even after heating to 900°C, the IR spectral features attributed to Si (Al)-O stretching and bending vibration modes do not show significant differences from those of unheated zeolites.

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 40u2009GPa. 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 ~25u2009GPa. 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.

EXAMINING STRUCTURAL AND RELATED SPECTRAL CHANGE IN MARS-RELEVANT PHYLLOSILICATES AFTER EXPERIMENTAL IMPACTS BETWEEN 10–40 GPA

Accurate clay mineral identification is key to understanding past aqueous activity on Mars, but martian phyllosilicates are old (>3.5 Ga) and have been heavily bombarded by meteoroid impacts. Meteoroid impacts can alter clay mineral structures and spectral signatures, making accurate remote sensing identifications challenging. This paper uses nuclear magnetic resonance (NMR) spectroscopy to examine the short-range structural deformation induced in clay mineral samples of known composition by artificial impacts and calcination. Structural changes are then related to changes in the visible-near infrared (VNIR) and mid-infrared (MIR) spectra of these clay mineral samples. The susceptibility of phyllosilicates to structural deformation after experimental impacts varies by structure. Experimental results showed that trioctahedral, Mg(II)-rich saponite was structurally resilient up to peak pressures of 39.8 GPa and its unchanged post-impact spectra reflected this. Experimental data on kaolinite showed that this Al(III)-rich, dioctahedral phyllosilicate was susceptible to structural alteration at peak pressures ⩾ 25.1 GPa. This result is similar to previously reported experimental results on the Fe(III)-rich dioctahedral smectite nontronite, suggesting that dioctahedral phyllosilicates may be more susceptible to shock-induced structural deformation than trioctahedral phyllosilicates. The octahedral vacancies present in dioctahedral phyllosilicates may drive this increased susceptibility to deformation relative to trioctahedral phyllosilicates with fully occupied octahedral sheets. Thermal alteration accompanies shock in meteoroid impacts, but shock differs from thermal alteration. NMR spectroscopy showed that structural deformation in thermally altered phyllosilicates differs from that found in shocked phyllosilicates. Similar to shock, dioctahedral phyllosilicates are also more susceptible to thermal alteration. This differential susceptibility to impact-alteration may help explain generic smectite identifications from heavily bombarded terrains on Mars.

The Martian subsurface as a potential window into the origin of life

Few traces of Earth’s geologic record are preserved from the time of life’s emergence, over 3,800 million years ago. Consequently, what little we understand about abiogenesis — the origin of life on Earth — is based primarily on laboratory experiments and theory. The best geological lens for understanding early Earth might actually come from Mars, a planet with a crust that’s overall far more ancient than our own. On Earth, surface sedimentary environments are thought to best preserve evidence of ancient life, but this is mostly because our planet has been dominated by high photosynthetic biomass production at the surface for the last ~2,500 million years or more. By the time oxygenic photosynthesis evolved on Earth, Mars had been a hyperarid, frozen desert with a surface bombarded by high-energy solar and cosmic radiation for more than a billion years, and as a result, photosynthetic surface life may never have occurred on Mars. Therefore, one must question whether searching for evidence of life in Martian surface sediments is the best strategy. This Perspective explores the possibility that the abundant hydrothermal environments on Mars might provide more valuable insights into life’s origins.Ancient hydrothermal deposits formed in the Martian subsurface may be the best targets for finding evidence for ancient life on Mars, and clues about the origin of life on Earth.

Elevated olivine weathering rates and sulfate formation at cryogenic temperatures on Mars

Large Hesperian-aged (~3.7u2009Ga) layered deposits of sulfate-rich sediments in the equatorial regions of Mars have been suggested to be evidence for ephemeral playa environments. But early Mars may not have been warm enough to support conditions similar to what occurs in arid environments on Earth. Instead cold, icy environments may have been widespread. Under cryogenic conditions sulfate formation might be blocked, since kinetics of silicate weathering are typically strongly retarded at temperatures well below 0u2009°C. But cryo-concentration of acidic solutions may counteract the slow kinetics. Here we show that cryo-concentrated acidic brines rapidly chemically weather olivine minerals and form sulfate minerals at temperatures as low as −60u2009°C. These experimental results demonstrate the viability of sulfate formation under current Martian conditions, even in the polar regions. An ice-hosted sedimentation and weathering model may provide a compelling description of the origin of large Hesperian-aged layered sulfate deposits on Mars.Sulphate-rich sediments have been taken as evidence of surface water on Mars. Here, the authors show that cryo-concentrated brines chemically weather olivine minerals forming sulfate minerals at up to −60u2009°C, showing that cryogenic weathering and sulfate formation can occur under current Martian conditions.

Shock metamorphism of clay minerals on Mars by meteor impact

A large fraction of clay minerals detected on Mars by infrared remote sensing represent materials exhumed from the subsurface by meteor impact, begging the question of whether the infrared features used to detect the clays are affected by shock associated with the impacts. We used X-ray diffraction and infrared and Mossbauer spectroscopy to evaluate the mineralogy of five clay minerals after experimentally shocking them to six shock pressures from ~10-40 GPa. The shocked clays exhibit three main relevant shock effects: 1) an overall decrease in infrared spectral contrast in the impact-fragmented materials, 2) oxidation of Fe in ferrous clays, and 3) loss of some spectral structure in relatively well-ordered clays such as kaolinite. Other than the widespread oxidation of ferrous clays, shock metamorphism likely has little effect on the accurate interpretation of clay mineralogy on Mars from remote sensing data. However, we are able to identify rare cases of extreme shock in some martian clay deposits.