The geosphere and biosphere coevolved and influenced Earth's biological and mineralogical diversity. Changing redox conditions influenced the availability of different transition metals, which are essential components in the active sites of oxidoreductases, proteins that catalyze electron transfer reactions across the tree of life. Despite its relatively low abundance in the environment, cobalt (Co) is a unique metal in biology due to its importance to a wide range of organisms as the metal center of vitamin B-12 (aka cobalamin, Cbl). Cbl is vital to multiple methyltransferase enzymes involved in energetically favorable metabolic pathways. It is unclear how Co availability is linked to mineral evolution and weathering processes. Here we examine important biological functions of Co, as well as chemical and geological factors that may have influenced the utilization of Co early in the evolution of life. Only 66 natural minerals are known to contain Co as an essential element. However, Co is incorporated as a minor element in abundant rock-forming minerals, potentially representing a reliable source of Co as a trace element in marine systems due to weathering processes. We developed a mineral weathering model that indicates that dissolved Co was potentially more bioavailable in the Archean ocean under low S conditions than it is today. Mineral weathering, redox chemistry, Co complexation with nitrogen-containing organics, and hydrothermal environments were crucial in the incorporation of Co in primitive metabolic pathways. These chemical and geological characteristics of Co can inform the biological utilization of other trace metals in early forms of life.

Dissolved ions present in an aqueous environment may significantly improve biomolecule attachment at mineral surfaces through the formation of cooperative surface complexes. To test whether this phenomenon results in the selective adsorption of an organic species, we conducted batch adsorption experiments with an equimolar mixture of the amino acids aspartate, glycine, lysine, leucine, and phenylalanine onto powdered brucite [Mg(OH)(2)] at pH 10.2. We performed the batch experiments in triplicate both without and with 4.1 mM CaCl2. In experiments without CaCl2, we observed that up to 0.7 mu mol m(-2) of aspartate and about 0.4 mu mol m(-2) each of the remaining four amino acids adsorbed onto brucite. When we added CaCl2, we found that up to 1.6 mu mol m(-2) of aspartate selectively adsorbed onto the brucite surface relative to between 0.2 and 0.3 mu mol m(-2) of the other amino acids. We measured the brucite particle surface charge to be slightly positive without added CaCl2, but the surface charge becomes significantly more positive in the presence of CaCl2. Our results suggest that negatively charged molecules selectively and cooperatively adsorb onto brucite when CaCl2 is added to the system. This study emphasizes the importance of the dissolved ionic profile of a geochemical environment when evaluating the role of mineral surfaces in the evolution of prebiotic chemistry. The presence of dissolved ions at a mineral-water interface can selectively enhance the adsorption and concentration of specific molecules, which may serve as a key process in molecular self-organization and the assembly of proteins that are composed of metal-ligand complexes.

The unit-cell dimensions and crystal structure of kyanite at various pressures up to 4.56 GPa were refined from single-crystal X-ray diffraction data. The bulk modulus is 193(1) GPa, assuming K' = 4.0. Calculated unit-strain tensors show that kyanite exhibits more isotropic compressibility than andalusite or sillimanite. The most and least compressible directions in the kyanite structure correspond approximately to the most and the least thermally expandable directions. The analysis of the distortion of the closest packing in kyanite indicates that the most compressible direction of the structure (along [012]) corresponds to the direction along which the closest-packed O monolayers are stacked. The bulk moduli for the A11, A12, A13, and A14 octahedra are 274(43), 207(14), 224(26), and 281(24) GPa, respectively, and those for the Si1 and Si2 tetrahedra are 322(80) and 400(95) GPa, respectively. Four AlO6 octahedra that all become less distorted at higher pressures do not display clearly dominant compression directions. The average unshared O-O distance for each octahedron is considerably more compressible than the shared O-O distance. The high-pressure behaviors of the All and A14 octahedra are very similar but different from those of the A12 and A13 octahedra. Bulk moduli for the three Al2SiO5 polymorphs (kyanite, sillimanite, and andalusite), as well as those for the AlO6 octahedra in their structures, appear to decrease linearly as their volumes increase. The significantly larger bulk modulus and more isotropic compressibility for kyanite than for andalusite or sillimanite are a consequence of the nearly cubic close-packed arrangement of O atoms and the complex edge-sharing among four distinct AlO6 octahedra in the kyanite structure.