Effects of Organic Compounds on Dissolution of the Phosphate Minerals Chlorapatite, Whitlockite, Merrillite, and Fluorapatite: Implications for Interpreting Past Signatures of Organic Compounds in Rocks, Soils and Sediments

Phosphate is an essential nutrient for life on Earth, present in adenosine triphosphate (ATP), deoxyribonucleic acid (DNA), ribonucleic acid (RNA), and phospholipid membranes. Phosphorus does not have a significant volatile phase, and its release from minerals is therefore critical to its bioavailability. Organic ligands can enhance phosphate release from minerals relative to release in inorganic solutions, and phosphorus depletion in paleosols has consequently been used as a signature of the presence of ligands secreted by terrestrial organisms on early Earth. We performed batch dissolution experiments of the Mars-relevant phosphate minerals merrillite, whitlockite, chlorapatite, and fluorapatite in solutions containing organic compounds relevant to Mars. We also analyzed these phosphate minerals using the ChemCam laboratory instrument at Los Alamos, providing spectra of end-member phosphate phases that are likely present on the surface of Mars. Phosphate release rates from chlorapatite, whitlockite, and merrillite were enhanced by mellitic, oxalic, succinic, and acetic acids relative to inorganic controls by as much as >35 × . The effects of the organic compounds could be explained by the denticity of the ligand, the strength of the complex formed with calcium, and the solution saturation state. Merrillite, whitlockite, and chlorapatite dissolution rates were more strongly enhanced by acetic and succinic acids relative to inorganic controls (as much as >10 ×) than were fluorapatite dissolution rates (≲2 ×). These results suggest that depletion of phosphate in soils, rocks or sediments on Mars could be a sensitive indicator of the presence of organic compounds.