Ocean-atmosphere interactions in the emergence of complexity in simple chemical systems.

The prebiotic conversion of simple organic molecules into complex biopolymers necessary for life can only have emerged on a stage set by geophysics. The transition between "prebiotic soup," the diverse mixture of small molecules, and complex, self-replicating organisms requires passing through the bottleneck of fundamental chemistry. In this Account, we examine how water-air interfaces, namely, the surfaces of lakes, oceans, and atmospheric aerosols on ancient Earth, facilitated the emergence of complex structures necessary for life. Aerosols are liquid or solid suspensions in air with a broad, power law size distribution. Collectively, these globally distributed atmospheric particles have an enormous surface area. Organic films at the interface between water and air offer advantages for biomolecular synthesis compared with the bulk and can simultaneously participate in the folding of biopolymers into primitive enclosed structures. We survey the advantages of the water-air interface for prebiotic chemistry in a geophysical context from three points of view. We examine the formation of biopolymers from simple organic precursors and describe the necessity and availability of enclosures. In addition, we provide a statistical mechanical approach to natural selection and emergence of complexity that proposes a link between these molecular mechanisms and macroscopic scales. Very large aerosol populations were ubiquitous on ancient Earth, and the surfaces of lakes, oceans, and atmospheric aerosols would have provided an auspicious environment for the emergence of complex structures necessary for life. These prebiotic reactors would inevitably have incorporated the products of chemistry into their anhydrous, two-dimensional organic films in the three-dimensional fluids of the gaseous atmosphere and the liquid ocean. The untrammeled operation of natural selection on these aerosols provided the likely location where condensation reactions could form biopolymers by elimination of water. The fluctuating exposure of the large, recycling aerosol populations to radiation, pressure, temperature, and humidity over geological time allows complexity to emerge from simple molecular precursors. We propose an approach that connects chemical statistical thermodynamics and the macroscopic world of the planetary ocean and atmosphere.