Stability against freezing of aqueous solutions on early Mars.

Many features of the Martian landscape are thought to have been formed by liquid water flow and water-related mineralogies on the surface of Mars are widespread and abundant. Several lines of evidence, however, suggest that Mars has been cold with mean global temperatures well below the freezing point of pure water. Martian climate modellers considering a combination of greenhouse gases at a range of partial pressures find it challenging to simulate global mean Martian surface temperatures above 273 K, and local thermal sources cannot account for the widespread distribution of hydrated and evaporitic minerals throughout the Martian landscape. Solutes could depress the melting point of water in a frozen Martian environment, providing a plausible solution to the early Mars climate paradox. Here we model the freezing and evaporation processes of Martian fluids with a composition resulting from the weathering of basalts, as reflected in the chemical compositions at Mars landing sites. Our results show that a significant fraction of weathering fluids loaded with Si, Fe, S, Mg, Ca, Cl, Na, K and Al remain in the liquid state at temperatures well below 273 K. We tested our model by analysing the mineralogies yielded by the evolution of the solutions: the resulting mineral assemblages are analogous to those actually identified on the Martian surface. This stability against freezing of Martian fluids can explain saline liquid water activity on the surface of Mars at mean global temperatures well below 273 K.

Long lasting habitable periods in Gale crater constrained by glauconitic clays.

In situ investigations by the Mars Science Laboratory, Curiosity rover, have confirmed the presence of an ancient lake in Gale crater for up to 10 million years. The lake was filled with sediments that eventually converted to a compacted sandstone. However, it remains unclear whether the infilling of the lake was the result of background sedimentation processes or represents punctual flooding events in a largely isolated lake. Here we used the XRD data obtained with the Chemistry and Mineralogy instrument (CheMin), on board the Curiosity rover, to characterize the degree of disorder of clay minerals in the Murray formation (MF) at Gale crater. Our analysis shows that they are structurally and compositionally related to glauconitic clays, which are a sensitive proxy of quiescent conditions in liquid bodies for extended periods of time. Such results provide evidence of long periods of extremely low sedimentation in an ancient brackish lake on Mars, signature of an aqueous regime with slow evaporation at low temperatures. More in general, the identification of lacustrine glauconitic clays on Mars provides a key parameter in the characterization of aqueous Martian paleoenvironments that may once have harbored life.

Constraining the preservation of organic compounds in Mars analog nontronites after exposure to acid and alkaline fluids.

The presence of organic matter in lacustrine mudstone sediments at Gale crater was revealed by the Mars Science Laboratory Curiosity rover, which also identified smectite clay minerals. Analogue experiments on phyllosilicates formed under low temperature aqueous conditons have illustrated that these are excellent reservoirs to host organic compounds against the harsh surface conditions of Mars. Here, we evaluate whether the capacity of smectites to preserve organic compounds can be influenced by a short exposure to different diagenetic fluids. We analyzed the stability of glycine embedded within nontronite samples previously exposed to either acidic or alkaline fluids (hereafter referred to as "treated nontronites") under Mars-like surface conditions. Analyses performed using multiple techniques showed higher photodegradation of glycine in the acid-treated nontronite, triggered by decarboxylation and deamination processes. In constrast, our experiments showed that glycine molecules were preferably incorporated by ion exchange in the interlayer region of the alkali-treated nontronite, conferring them a better protection against the external conditions. Our results demonstrate that smectite previously exposed to fluids with different pH values influences how glycine is adsorbed into their interlayer regions, affecting their potential for preservation of organic compounds under contemporary Mars surface conditions.

Surface clay formation during short-term warmer and wetter conditions on a largely cold ancient Mars.

The ancient rock record for Mars has long been at odds with climate modelling. The presence of valley networks, dendritic channels and deltas on ancient terrains points towards running water and fluvial erosion on early Mars1, but climate modelling indicates that long-term warm conditions were not sustainable2. Widespread phyllosilicates and other aqueous minerals on the Martian surface3-6 provide additional evidence that an early wet Martian climate resulted in surface weathering. Some of these phyllosilicates formed in subsurface crustal environments5, with no association with the Martian climate, while other phyllosilicate-rich outcrops exhibit layered morphologies and broad stratigraphies7 consistent with surface formation. Here, we develop a new geochemical model for early Mars to explain the formation of these clay-bearing rocks in warm and wet surface locations. We propose that sporadic, short-term warm and wet environments during a generally cold early Mars enabled phyllosilicate formation without requiring long-term warm and wet conditions. We conclude that Mg-rich clay-bearing rocks with lateral variations in mixed Fe/Mg smectite, chlorite, talc, serpentine and zeolite occurrences formed in subsurface hydrothermal environments, whereas dioctahedral (Al/Fe3+-rich) smectite and widespread vertical horizonation of Fe/Mg smectites, clay assemblages and sulphates formed in variable aqueous environments on the surface of Mars. Our model for aluminosilicate formation on Mars is consistent with the observed geological features, diversity of aqueous mineralogies in ancient surface rocks and state-of-the-art palaeoclimate scenarios.

Mineral paragenesis on Mars: The roles of reactive surface area and diffusion.

Geochemical models of secondary mineral precipitation on Mars generally assume semiopen systems (open to the atmosphere but closed at the water-sediment interface) and equilibrium conditions. However, in natural multicomponent systems, the reactive surface area of primary minerals controls the dissolution rate and affects the precipitation sequences of secondary phases, and simultaneously, the transport of dissolved species may occur through the atmosphere-water and water-sediment interfaces. Here we present a suite of geochemical models designed to analyze the formation of secondary minerals in basaltic sediments on Mars, evaluating the role of (i) reactive surface areas and (ii) the transport of ions through a basalt sediment column. We consider fully open conditions, both to the atmosphere and to the sediment, and a kinetic approach for mineral dissolution and precipitation. Our models consider a geochemical scenario constituted by a basin (i.e., a shallow lake) where supersaturation is generated by evaporation/cooling and the starting point is a solution in equilibrium with basaltic sediments. Our results show that cation removal by diffusion, along with the input of atmospheric volatiles and the influence of the reactive surface area of primary minerals, plays a central role in the evolution of the secondary mineral sequences formed. We conclude that precipitation of evaporites finds more restrictions in basaltic sediments of small grain size than in basaltic sediments of greater grain size.

Tracking the weathering of basalts on Mars using lithium isotope fractionation models.

Lithium (Li), the lightest of the alkali elements, has geochemical properties that include high aqueous solubility (Li is the most fluid mobile element) and high relative abundance in basalt-forming minerals (values ranking between 0.2 and 12 ppm). Li isotopes are particularly subject to fractionation because the two stable isotopes of lithium-7Li and 6Li-have a large relative mass difference (∼15%) that results in significant fractionation between water and solid phases. The extent of Li isotope fractionation during aqueous alteration of basalt depends on the dissolution rate of primary minerals-the source of Li-and on the precipitation kinetics, leading to formation of secondary phases. Consequently, a detailed analysis of Li isotopic ratios in both solution and secondary mineral lattices could provide clues about past Martian weathering conditions, including weathering extent, temperature, pH, supersaturation, and evaporation rate of the initial solutions in contact with basalt rocks. In this paper, we discuss ways in which Martian aqueous processes could have lead to Li isotope fractionation. We show that Li isotopic data obtained by future exploration of Mars could be relevant to highlighting different processes of Li isotopic fractionation in the past, and therefore to understanding basalt weathering and environmental conditions early in the planet's history.

Pyrite nanoparticles as a Fenton-like reagent for in situ remediation of organic pollutants.

The Fenton reaction is the most widely used advanced oxidation process (AOP) for wastewater treatment. This study reports on the use of pyrite nanoparticles and microparticles as Fenton reagents for the oxidative degradation of copper phthalocyanine (CuPc) as a representative contaminant. Upon oxidative dissolution in water, pyrite (FeS2) particles can generate H2O2 at their surface while simultaneously promoting recycling of Fe(3+) into Fe(2+) and vice versa. Pyrite nanoparticles were synthesized by the hot injection method. The use of a high concentration of precursors gave individual nanoparticles (diameter: 20 nm) with broader crystallinity at the outer interfaces, providing a greater number of surface defects, which is advantageous for generating H2O2. Batch reactions were run to monitor the kinetics of CuPc degradation in real time and the amount of H2O2. A markedly greater degradation of CuPc was achieved with nanoparticles as compared to microparticles: at low loadings (0.08 mg/L) and 20 h reaction time, the former enabled 60% CuPc removal, whereas the latter enabled only 7% removal. These results confirm that the use of low concentrations of synthetic nanoparticles can be a cost effective alternative to conventional Fenton procedures for use in wastewater treatment, avoiding the potential risks caused by the release of heavy metals upon dissolution of natural pyrites.