Dioctahedral Phyllosilicates Versus Zeolites and Carbonates Versus Zeolites Competitions as Constraints to Understanding Early Mars Alteration Conditions

Viennet et al. (2017) Journal of Geophysical Research: Planets, Volume 122, Issue 11, pp. 2328-2343

Abstract: Widespread occurrence of Fe,Mg-phyllosilicates has been observed on Noachian Martian terrains. Therefore, the study of Fe,Mg-phyllosilicate formation, in order to characterize early Martian environmental conditions, is of particular interest to the Martian community. Previous studies have shown that the investigation of Fe,Mg-smectite formation alone helps to describe early Mars environmental conditions, but there are still large uncertainties in terms of pH range, oxic/anoxic conditions, etc. Interestingly, carbonates and/or zeolites have also been observed on Noachian surfaces in association with the Fe,Mg-phyllosilicates. Consequently, the present study focuses on the dioctahedral/trioctahedral phyllosilicate/carbonate/zeolite formation as a function of various CO2 contents (100% N2, 10% CO2/90% N2, and 100% CO2), from a combined approach including closed system laboratory experiments for 3 weeks at 120°C and geochemical simulations. The experimental results show that as the CO2 content decreases, the amount of dioctahedral clay minerals decreases in favor of trioctahedral minerals. Carbonates and dioctahedral clay minerals are formed during the experiments with CO2. When Ca-zeolites are formed, no carbonates and dioctahedral minerals are observed. Geochemical simulation aided in establishing pH as a key parameter in determining mineral formation patterns. Indeed, under acidic conditions dioctahedral clay minerals and carbonate minerals are formed, while trioctahedral clay minerals are formed in basic conditions with a neutral pH value of 5.98 at 120°C. Zeolites are favored from pH ≳ 7.2. The results obtained shed new light on the importance of dioctahedral clay minerals versus zeolites and carbonates versus zeolites competitions to better define the aqueous alteration processes throughout early Mars history.


Experimental hydrothermal alteration of basaltic glass with relevance to Mars.

Sætre, C. et al. (2019).  Meteoritics and Planetary Science.  ISSN 1086-9379.

Phyllosilicates, carbonates, zeolites, and sulfates on Mars give clues about the planet's past environmental conditions, but little is known about the specific conditions in which these minerals formed within the crust and at the surface. The aim of the present study was to gain increased understanding on the formation of secondary phases by hydrothermal alteration of basaltic glass. The reaction processes were studied under varying conditions (temperature, pCO2, water:rock ratio, and fluid composition) with relevance to aqueous hydrothermal alteration in fully and partly saturated Martian basalt deposits. Analyses made on reaction products using X‐ray diffraction (XRD) and scanning electron microscope (SEM) were compared with near infrared spectroscopy (NIR) to establish relative detectability and spectral signatures. This study demonstrates that comparable alteration minerals (phyllosilicates, carbonates, zeolites) form from vapor condensing on mineral surfaces in unsaturated sediments and not only in fully water‐saturated sediments. In certain environments where water vapor might be present, it can alter the basaltic bedrock to a suite of authigenic phases similar to those observed on the Martian surface. For the detection of the secondary phases, XRD and SEM‐EDS were found to be superior to NIR for detecting and characterizing zeolites. The discrepancy in detectability of zeolites between NIR and XRD/SEM‐EDS might indicate that zeolites on Mars are more abundant than previously thought.


Planetary Terrestrial Analogues Library (PTAL) project: Raman data overview

Veneranda et al (2019)

The multianalytical study of terrestrial analogues is a useful strategy to deepen the knowledge about the geological and environmental evolution of Mars and other extraterrestrial bodies. In spite of the increasing importance that laser‐induced breakdown spectroscopy (LIBS), near‐infrared spectroscopy (NIR), and Raman techniques are acquiring in the field of space exploration, there is a lack Web‐based platform providing free access to a wide multispectral database of terrestrial analogue materials. The Planetary Terrestrial Analogues Library (PTAL) project aims at responding to this critical need by developing and providing free Web accessibility to LIBS, NIR, and Raman data from more than 94 terrestrial analogues selected according to their congruence with Martian geological contexts. In this framework, the present manuscript provides the scientific community with a complete overview of the over 4,500 Raman spectra collected to feed the PTAL database. Raman data, obtained through the complementary use of laboratory and spacecraft‐simulator systems, confirmed the effectiveness of this spectroscopic technique for the detection of major and minor mineralogical phases of the samples, the latter being of critical importance for the recognition of geological processes that could have occurred on Mars and other planets. In light of the forthcoming missions to Mars, the results obtained through the Raman Laser Spectrometer (RLS) ExoMars Simulator offer a valuable insight on the scientific outcome that could derive from the RLS spectrometer that will soon land on Mars as part of the ExoMars rover payload.


Spectroscopic study of olivine-bearing rocks and its relevance to the ExoMars rover mission

Veneranda et al, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 223 (2019) 117360

We present the compositional analysis of three terrestrial analogues of Martian olivine-bearing rocks derived from both laboratory and flight-derived analytical instruments. In the first step, state-of-the-art spectroscopic (XRF, NIR and Raman) and diffractometric (XRD) laboratory systemswere complementary used. Besides providing a detailed mineralogical and geochemical characterization of the samples, results comparison shed light on the advantages ensured by the combined use of Raman and NIR techniques, being these the spectroscopic instruments that will soon deploy (2021) on Mars as part of the ExoMars/ESA rover payload. In order to extrapolate valuable indicators of the mineralogical data that could derive from the ExoMars/Raman Laser Spectrometer (RLS), laboratory results were then compared with the molecular data gathered through the RLS ExoMars Simulator. Beside correctly identifying all major phases (feldspar, pyroxene and olivine), the RLS ExoMars Simulator confirmed the presence of additional minor compounds (i.e. hematite and apatite) that were not detected by complementary techniques. Furthermore, concerning the in-depth study of olivine grains, the RLS ExoMars simulator
was able to effectively detect the shifting of the characteristic double peak around 820 and 850 cm−1, from which the Fe\\Mg content of the analyzed crystals can be extrapolated. Considering that olivine is one of the main mineral phases of the ExoMars landing site (Oxia Planum), this study suggests that the ExoMars/RLS system has the potential to provide detailed information about the elemental composition of olivine on Mars.


Detection of Carbonates in Martian Weathering Profiles

Bultel et al (2019)

Noachian surfaces on Mars exhibit vertical assemblages of weathering horizons termed as weathering profiles; this indicates that surface water caused alteration of the rocks that required a different, warmer climate than today. Evidence of this early Martian climate with CO2 vapor as the main component causing greenhouse warming has been challenged by the lack of carbonate in these profiles. Here we report the analysis of Compact Reconnaissance Imaging Spectrometer for Mars L‐detector data leading to the detections of carbonates using a spectral signature exclusively attributed to them. The carbonates are collocated with hydroxylated minerals in weathering profiles over the Martian surface. The origin of CO2 for the formation of carbonates could be the atmosphere. The widespread distribution of weathering profiles with carbonates over the surface of the planet suggest global interactions between fluids containing carbonate/bicarbonate ions with the surface of Mars in the presence of atmospheric water until around 3.7 billion years ago.


Deposition of >3.7 Ga clay-rich strata of the Mawrth Vallis Group, Mars, in lacustrine, alluvial, and aeolian environments

Lowe et al. (2019) GSA Bulletin

The presence of abundant phyllosilicate minerals in Noachian (>3.7 Ga) rocks on Mars has been taken as evidence that liquid water was stable at or near the surface early in martian history. This study investigates some of these clay-rich strata exposed in crater rim and inverted terrain settings in the Mawrth Vallis region of Mars. In Muara crater the 200-m-thick, clay-rich Mawrth Vallis Group (MVG) is subdivided into five informal units numbered 1 (base) to 5 (top). Unit 1 consists of interbedded sedimentary and volcanic or volcaniclastic units showing weak Fe/Mg-smectite alteration deposited in a range of subaerial depositional settings. Above a major unconformity eroded on Unit 1, the dark-toned sediments of Unit 2 and lower Unit 3 are inferred to represent mainly wind-blown sand. These are widely interlayered with and draped by thin layers of light-toned sediment representing fine suspended-load aeolian silt and clay. These sediments show extensive Fe/Mg-smectite alteration, probably reflecting subaerial weathering. Upper Unit 3 and units 4 and 5 are composed of well-layered, fine-grained sediment dominated by Al-phyllosilicates, kaolinite, and hydrated silica. Deposition occurred in a large lake or arm of a martian sea. In the inverted terrain 100 km to the NE, Unit 4 shows very young slope failures suggesting that the clay-rich sediments today retain a significant component of water ice. The MVG provides evidence for the presence of large, persistent standing bodies of water on early Mars as well as a complex association of flanking shoreline, alluvial, and aeolian systems. Some of the clays, especially the Fe/Mg smectites in upper units 1 and 2 appear to have formed through subaerial weathering whereas the aluminosilicates, kaolinite, and hydrated silica of units 3, 4, and 5 formed mainly through alteration of fine sediment in subaqueous environments.


Experimental reproduction of the martian weathering profiles argues for a dense Noachian CO2 atmosphere.

Viennet, J.-C., B. Bultel, S.C. Werner (2019)

On Mars, mineral sequences have been detected and they are composed of a top layer of Al-rich clay minerals, then (Al, Fe)-rich clay minerals and a bottom layer composed of (Mg, Fe)-rich clay minerals. By analogy with Earth, such sequences are interpreted as weathering profiles formed by the interaction of acidic solutions in equilibrium with the atmosphere and the parent rock. Thus, understanding of the aqueous solution composition leading to the above mineral description allows deciphering the atmosphere composition. We designed an experimental column system with three levels containing powdered basaltic rock to test the influence of different acidic fluids on the mineralogical formation. Five solutions were used: H2SO4 and HCl at pH 3 in equilibrium with N2 atmosphere, pure water in equilibrium with 0.1 and 1 atmospheric pressure CO2 leading to pH values of 3.9 and 4.4, respectively and a H2SO4 solution at pH 3 in equilibrium with 0.1 atmospheric pressure CO2 leading to a pH value of 2.98. The results obtained show that the content of Al-rich clay minerals and the evolution from Al, (Al, Fe) to (Fe, Mg)-rich clay minerals formed are better reproduced with an originally high pCO2. Hence, we suggest that acidic alteration driven by a dense CO2 atmosphere reproduced better the observed martian weathering profiles. The experiments involving CO2 led to the formation of carbonates. Their identification by near infrared (NIR) detection methods is challenged, because the laboratory NIR spectra acquired on the experimental products show that: (i) the absorption bands related to carbonates are very weak, and (ii) the strongest feature at 3.95 μm is beyond the CRISM NIR range. Such carbonate formation is consistent with the recent carbonate detection at a planetary scale in weathering profiles, which goes toward that the weathering profiles could have been formed under a dense CO2-rich atmosphere as suggested also by climatic models.