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.