The endoergic nature of protein and nucleic acid assembly in aqueous media presents two questions that are fundamental to the understanding of life’s origins: (i) how did the polymers arise in an aqueous prebiotic world; and (ii) once formed in some manner, how were they sufficiently persistent to engage in further chemistry. We propose here a quantitative resolution of these issues that evolved from recent accounts in which RNA-like polymers were produced in evaporation/rehydration cycles. The equilibrium N_m + N_n ↔ N_m+n + H₂O is endoergic by about 3.3 kcal/mol for polynucleotide formation, and the system thus lies far to the left in the starting solutions. Kinetic simulations of the evaporation showed that simple Le Châtelier’s principle shifts were insufficient, but the introduction of oligomer-stabilizing factors of 5–10 kcal/mol both moved the process to the right and respectively boosted and retarded the elongation and hydrolysis rates. Molecular crowding and excluded volume effects in present-day cells yield stabilizing factors of that order, and we argue here that the crowded conditions in the evaporites generate similar effects. Oligomer formation is thus energetically preferred in those settings, but the process is thwarted in each evaporation step as diffusion becomes rate limiting. Rehydration dissipates disordered oligomer clusters in the evaporites, however, and subsequent dry/wet cycling accordingly “ratchets up” the system to an ultimate population of kinetically trappedthermodynamically preferred biopolymers.

The significance of Wächtershäuser's iron-sulfur world to the origin of life and the limits to its notional autocatalytic cycles are examined in kinetic simulations of the chain polymerization sequence: primitive materials-->amino acids-->oligomers. The simulations were run for the formation of all oligomers up to the 20-mer over a 1 Gy interval from the end of the period of heavy bombardment, during which period life emerged. Upper-limit rate constant estimates developed from the studies of Huber and Wächtershäuser were employed. The simulations showed that oligomer production consistent with life's start within that interval emerges only with an autocatalyst exhibiting a catalytic proficiency comparable to that of contemporary enzymes. The simulations, moreover, ignored likely thermodynamic and statistical burdens which, if included, would have led to the need for catalytic capacities well in excess of those in present-day enzymes. Prebiotic oligomers with such levels of activity are clearly not likely, and it is apparent that the iron-sulfur scheme could not have played a role in life's beginnings.

SRI conducted a study on the hydrothermolytic disposal of energetic materials (EMs) using a continuous flow reactor which was designed, assembled and tested in studies of the hydrothermolysis of ammonium picrate at 360 deg C. The dissolution study showed that the TNT solubility in water increased by a factor of about 200 from 25 deg C to 200 deg C. The literature shows that the solubility of benzene in water increases by a factor of about 50 over the same interval and benzene becomes completely soluble at about 300 deg C. Therefore, the complete dissolution of TNT in water at temperatures no greater than 300 deg C. Calculations of the critical radii for explosion were made for TNT, HMS, and PETN at 200-350 deg C based on relations for kinetics of self heating. TNT has a critical radius of 0.019 cm at 350 deg C, meaning that spherical particles exceeding this radius will self heat to explosion at 350 deg C.