Study of Ferrocyanide Adsorption onto Different Minerals as Prebiotic Chemistry Assays

Considered one of the most promising building blocks of life on primitive Earth, cyanide and its complexes are likely to have played an important role in the emergence of life on the planet. Investigation into cyanide on Earth has primarily considered high concentrations, but the cyanide concentration in the oceans of prebiotic Earth was exceptionally low. Thus, Bernal's hypothesis has allowed investigators to work around this problem. We observed, however, that cyanide does not adsorb onto several minerals; therefore, ferrocyanide could be used as a cyanide source when adsorbed onto mineral surfaces to promote the synthesis of molecules of biological significance. When adsorbed onto bentonite, a mineral that has Fe³⁺ atoms in its interlayers, the formation of Prussian blue analog complexes occurs through endothermic reaction and with increased entropy. The adsorption of ferrocyanide onto kaolinite indicates an exothermic and outer-sphere interaction, which results in degeneracy breakdown for C ≡ N stretch energy into two new bands of FTIR-ATR spectrum. Magnetite, which has iron atoms in its structure, and ferrocyanide interactions have been observed by outer-sphere coordination as well as the formation of Prussian blue analogs, as confirmed by the appearance of a new doublet in the Mössbauer spectra and a broadband close to 750 nm at UV-visible spectroscopy. Magnetite and kaolinite experiments presented relevant results only when performed in seawater, which suggests the importance of seawater composition for prebiotic experiments. These obtained results prove that ferrocyanide interacts with minerals differently according to structure and composition and show that this complex, like the Prussian blue analogs, may have played a crucial role as a source of cyanide on primitive Earth.