Abiotic Formation of Calcium Oxalate under UV Irradiation and Implications for Biomarker Detection on Mars

A major objective in the exploration of Mars is to test the hypothesis that the planet has ever hosted life. Biogenic compounds, especially biominerals, are believed to serve as biomarkers in Raman-assisted remote sensing missions. However, the prerequisite for the development of these minerals as biomarkers is the uniqueness of their biogenesis. Herein, tetragonal bipyramidal weddellite, a type of calcium oxalate, is successfully achieved by UV-photolyzing pyruvic acid (PA). The as-prepared products are identified and characterized by micro-Raman spectroscopy and field emission scanning electron microscopy. Persistent mineralization of weddellite is observed with altering key experimental parameters, including pH, Ca²⁺ and PA concentrations. In particular, the initial concentration of PA can significantly influence the morphology of weddellite crystal. Oxalate acid is commonly of biological origin; thus calcium oxalate is considered to be a biomarker. However, our results reveal that calcium oxalate can be harvested by a UV photolysis pathway. Moreover, prebiotic sources of organics (e.g., PA, glycine, alanine, and aspartic acid) have been proven to be available through abiotic pathways. Therefore, our results may provide a new abiotic pathway of calcium oxalate formation. Considering that calcium oxalate minerals have been taken as biosignatures for the origin and early evolution of life on Earth and astrobiological investigations, its formation and accumulation by the photolysis of abiological organic compounds should be taken into account.