The Role of Calcite Dissolution and Halite Thermal Expansion as Secondary Salt Weathering Mechanisms of Calcite-Bearing Rocks in Marine Environments

This research focuses on the analysis of the influence of two secondary salt weathering processes on the durability of rocks exposed to marine environments: chemical dissolution of rock forming minerals and differential thermal expansion between halite and the hosting rock. These processes are scarcely treated in research compared to salt crystallisation. The methodology followed in this paper includes both in situ rock weathering monitoring and laboratory simulations. Four different calcite-bearing rocks (a marble, a microcrystalline limestone and two different calcarenites) were exposed during a year to a marine semiarid environment. Exposed samples show grain detachment, crystal edge corrosion, halite efflorescences and microfissuring. Crystal edge corrosion was also observed after the laboratory simulation during a brine immersion test. Calcite chemical dissolution causes a negligible porosity increase in all the studied rocks, but a significant modification of their pore size distribution. Laboratory simulations also demonstrate the deterioration of salt-saturated rocks during thermal cycles in climatic cabinet. Sharp differences between the linear thermal expansion of both a pure halite crystal and the different studied rocks justify the registered weight loss during the thermal cycles. The feedback between the chemical dissolution and differential thermal expansion, and the salt crystallisation of halite, contribute actively to the rock decay in marine environments.

Search for molecular biosignatures on Mars: laboratory simulations of UV irradiation of molecule-mineral complexes

<div> </div> <p><strong>Abstract</strong></p> <p>We present laboratory activities of preparation, characterization, and UV irradiation processing of Mars soil analogues, which are key to support both in situ exploration and sample return missions devoted to detection of molecular biosignatures on Mars.</p> <p>In detail we prepared analog mineral samples relevant to the landing sites of past, present and future Mars exploration missions, such as Gale Crater, Jezero Crater, and Oxia Planum. We doped these samples with a large variety of organic molecules (both biotic and prebiotic molecules) like amino acids, nucleotides, monosaccharides, aldehydes, lipids. We investigated molecular photostability under UV irradiation by monitoring in situ possible modifications of infrared spectroscopic features. These investigations provide pivotal information for ground analysis carried out by rovers on Mars.</p> <p><strong>Introduction</strong></p> <p>Laboratory simulations of Mars are key to support the scientific activity and technology development of life detection instruments on board present and upcoming rover missions such as Mars2020 Perseverance [1] and ExoMars2022 Rosalind Franklin [2]. Studies about the stability of organic molecules in a Martian-like environment allow us to explore the conditions for the preservation of molecular biosignatures and develop models for their degradation in the Martian geological record. A systematic study of the effects of UV radiation on a variety of molecule-mineral complexes mimicking Martian soil can be key for the selection of the most interesting samples to analyse in situ or/and collect for sample return. Testing the sensitivity of different techniques for detection of the diagnostic features of molecular biosignatures embedded into mineral matrices as a function of the molecular concentration helps the choice, design and operation of flight instruments, as well as the interpretation of data collected on the ground during mission operative periods.</p> <p><strong>Methods</strong></p> <p>Experimental analyses were conducted in the Astrobiology Laboratory at INAF-Astrophysical Observatory of Arcetri (Firenze, Italy). Laboratory activities pertain to: (i) synthesis of Mars soil analogues doped with organic compounds that are considered potential molecular biosignatures; (ii) UV-irradiation processing of the Mars soil analogues under Martian-like conditions; and (iii) spectroscopic characterization of the Mars soil analogues.</p> <p><strong>Results</strong></p> <p>Such studies have shown to be very informative in identifying mineral deposits most suitable for preservation of organic compounds, while highlighting the complementarity of different techniques for biomarkers detection, which is critical for ensuring the success of space missions devoted to the search for signs of life on Mars.</p> <p>We will present a series of laboratory results on molecular degradation caused by UV on Mars and possible application to detection of organics by Martian rovers [3,4,5,6]. In detail, we investigated the photostability of several amino acids like glycine, alanine, methionine, valine, tryptophan, phenylalanine, glutamic acid, prebiotic molecules like urea, deoxyribose and glycolaldehyde, and biomarkers like nucleotides and phytane adsorbed on relevant Martian analogs. We monitored the degradation of these molecule-mineral complexes through in situ spectroscopic analysis, investigating the reflectance properties of the samples in the NIR/MIR spectral region. Such spectroscopic characterization of molecular alteration products provides support for two upcoming robotic missions to Mars that will employ NIR spectroscopy to look for molecular biosignatures, through the instruments SuperCam on board Mars 2020, ISEM, Ma_MISS and MicrOmega on board ExoMars 2022.</p> <p><strong>Acknowledgements</strong></p> <p>This research was supported by the Italian Space Agency (ASI) grant agreement ExoMars n. 2017-48-H.0.</p> <p><strong>References</strong></p> <p>[1] Farley K. A. et al. (2020) Space Sci. Rev. 216, 142.</p> <p>[2] Vago, J. L. et al. (2017) Astrobiology 6, 309–347.</p> <p>[3] Fornaro T. et al. (2013) Icarus 226, 1068–1085.</p> <p>[4] Fornaro T. et al. (2018) Icarus 313, 38-60.</p> <p>[5] Fornaro T. et al. (2020) Front. Astron. Space Sci. 7:539289.</p> <p>[6] Poggiali G. et al. (2020) Front. Astron. Space Sci. 7:18.</p>

Dissolution of Different Reservoir Rocks by Organic Acids in Laboratory Simulations: Implications for the Effect of Alteration on Deep Reservoirs

Organic acids are important agents in the alteration of deep reservoirs. It is difficult, however, to assess the impact of organic acid alteration on deep reservoirs because different dissolution processes may occur during diagenesis. This study simulated the dissolution of three different types of reservoir rocks by acetic acid in a closed system and compared the mineral and elemental composition, surface morphology, pore structure, and water chemistry variations of the initial and altered samples. The study demonstrated that both micrite and sucrosic dolostone are strongly dissolved, losing about 20%–30% of their initial rock sample weights. Observation under SEM showed that the limestone dissolved homogenously, whereas the dolostone showed honeycomb-like dissolution. Both carbonate samples showed the development of large voids, including holes and cavities of micrometer scale, but nanopores of various sizes were blocked. In contrast, lithic arkose was heterogeneously altered, losing a weight proportion of about 13% by dissolution of calcite cement. These micrometer-scale microfissures were developed, but those nanometer-scale pores just varied in a narrow range of sizes. The volume increase in all three reservoir types is mainly attributed to the dissolution of carbonate minerals. In deep reservoirs, in situ generated organic acids can enlarge existing cavities in carbonates and develop microfissures in sandstones. The microfissure porosity in sandstone is limited but can increase through other geological processes such as overpressure. More importantly, these acids can maintain the acidity of pore waters, inhibit the precipitation of dissolved minerals, and help to preserve reservoir porosity. Although temperature plays an insignificant role in laboratory simulations, it influences both the generation and destruction processes of organic acids in deep reservoirs on geologic time scales and, thus, warrants further attention. The results provide a basis for recognizing the typical patterns of organic acid dissolution on different reservoir rocks and further suggest the potential role of organic acids in the formation and preservation of secondary porosity in deeply buried reservoirs.