SEM/Raman spectroscopy of clathrites as analogs of authigenic carbonates in ocean worlds

• Published in: Journal of Raman spectroscopy 2024-10, Vol.55 (10), p.1057-1066
• Main Authors: Dios‐Cubillas, Ana, Prieto‐Ballesteros, Olga, Nachtnebel, Manfred, Fitzek, Harald, Schröttner, Hartmuth
• Format: Article
• Language: English
• Subjects: Aragonite; Biochemical analysis; Calcite; Carbonate rocks; Carbonates; clathrate hydrates; clathrite; Dolomite; Earth analogs; Gas hydrates; Hydrates; Infrared spectroscopy; Mars missions; Microbiomes; Mineralogy; Near infrared radiation; ocean worlds; Pyrite; Raman; Raman spectroscopy; Scanning electron microscopy; SEM; Space missions; Subduction (geology); Texture
• ISSN: 0377-0486; 1097-4555
• DOI: 10.1002/jrs.6711

There is evidence from the near‐infrared observations of space missions of the presence of carbonates on the surface of several ocean worlds. However, their genesis remains unresolved. We investigate the hypothesis that these carbonates may be in the form of clathrites assuming that clathrate hydrates are stable phases in the crust and ocean of these ocean worlds. In order to support this, we studied a sample of a potential clathrite from the Hydrate Ridge cold seep (Cascadia Subduction Zone), the carbonate rock fossil of clathrate hydrates, as a terrestrial analogue. We characterised the mineralogy and texture of the sample by using a coupled confocal Raman microscope and scanning electron microscopy instrument with the aim of identifying possible geo‐ and biosignatures, which could be relevant for future missions of exploration to ocean worlds and Mars. Our results show that aragonite is the dominant mineral phase in the clathrite sample, but Mg‐calcite and dolomite were also identified. These three carbonates constitute a pattern related to clathrate hydrate formation and dissociation processes. Dolomite was defined as a biosignature of gas hydrate microbiomes because it was integrated within Mg‐calcite grains precipitated after clathrate hydrate dissociation. Nevertheless, no spectral changes were observed in Raman bands of carbonate minerals that would indicate the influence of clathrate hydrates in their genesis. We also observed that Raman band positions of the associated framboidal pyrites are a characteristic signature of the associated framboid‐like texture because its potential as biosignature may only be attributed by biochemical analysis. We present a correlative study on mineralogical and textural characteristics of clathrite by SEM/Raman spectroscopy. Learning to identify clathrites from other carbonates is key to space exploratiom focused on an astrobiological scope, as they would have the potential to preserve biosignatures and would reveal clues to a clathrate hydrate‐rich planetary geological interior.