This paper presents a reformulation of the submarine alkaline hydrothermal theory for the emergence of life in response to recent experimental findings. The theory views life, like other self-organizing systems in the Universe, as an inevitable outcome of particular disequilibria. In this case, the disequilibria were two: (1) in redox potential, between hydrogen plus methane with the circuit-completing electron acceptors such as nitrite, nitrate, ferric iron, and carbon dioxide, and (2) in pH gradient between an acidulous external ocean and an alkaline hydrothermal fluid. Both CO ₂ and CH ₄ were equally the ultimate sources of organic carbon, and the metal sulfides and oxyhydroxides acted as protoenzymatic catalysts. The realization, now 50 years old, that membrane-spanning gradients, rather than organic intermediates, play a vital role in life's operations calls into question the idea of “prebiotic chemistry.” It informs our own suggestion that experimentation should look to the kind of nanoengines that must have been the precursors to molecular motors—such as pyrophosphate synthetase and the like driven by these gradients—that make life work. It is these putative free energy or disequilibria converters, presumably constructed from minerals comprising the earliest inorganic membranes, that, as obstacles to vectorial ionic flows, present themselves as the candidates for future experiments. Key Words: Methanotrophy—Origin of life. Astrobiology 14, 308–343.

Irradiated ice-covered ocean worlds with rocky mafic mantles may provide the conditions needed to drive the emergence and maintenance of life. Alkaline hydrothermal springs—relieving the geophysical, thermal, and chemical disequilibria between oceans and tidally stressed crusts—could generate inorganic barriers to the otherwise uncontrolled and kinetically disfavored oxidation of hydrothermal hydrogen and methane. Ionic gradients imposed across these inorganic barriers, comprising iron oxyhydroxides and sulfides, could drive the hydrogenation of carbon dioxide and the oxidation of methane through thermodynamically favorable metabolic pathways leading to early life-forms. In such chemostatic environments, fuels may eventually outweigh oxidants. Ice-covered oceans are primarily heated from below, creating convection that could transport putative microbial cells and cellular cooperatives upward to congregate beneath an ice shell, potentially giving rise to a highly focused shallow biosphere. It is here where electron acceptors, ultimately derived from the irradiated surface, could be delivered to such life-forms through exchange with the icy surface. Such zones would act as “electron disposal units” for the biosphere, and occupants might be transferred toward the surface by buoyant diapirs and even entrained into plumes. Key Words: Biofilms—Europa—Extraterrestrial life—Hydrothermal systems. Astrobiology 17, 1265–1273.

The concept that life emerged where alkaline hydrogen-bearing submarine hot springs exhaled into the most ancient acidulous ocean was used as a working hypothesis to investigate the nature of precipitate membranes. Alkaline solutions at 25–70°C and pH between 8 and 12, bearing HS⁻±silicate, were injected slowly into visi-jars containing ferrous chloride to partially simulate the early ocean on this or any other wet and icy, geologically active rocky world. Dependent on pH and sulfide content, fine tubular chimneys and geodal bubbles were generated with semipermeable walls 4–100 μm thick that comprised radial platelets of nanometric mackinawite [FeS]±ferrous hydroxide [∼Fe(OH)₂], accompanied by silica and, at the higher temperature, greigite [Fe₃S₄]. Within the chimney walls, these platelets define a myriad of micropores. The interior walls of the chimneys host iron sulfide framboids, while, in cases where the alkaline solution has a pH>11 or relatively low sulfide content, their exteriors exhibit radial flanges with a spacing of ∼4 μm that comprise microdendrites of ferrous hydroxide. We speculate that this pattern results from outward and inward radial flow through the chimney walls. The outer Fe(OH)₂ flanges perhaps precipitate where the highly alkaline flow meets the ambient ferrous iron-bearing fluid, while the intervening troughs signal where the acidulous iron-bearing solutions could gain access to the sulfidic and alkaline interior of the chimneys, thereby leading to the precipitation of the framboids. Addition of soluble pentameric peptides enhances membrane durability and accentuates the crenulations on the chimney exteriors. These dynamic patterns may have implications for acid-base catalysis and the natural proton motive force acting through the matrix of the porous inorganic membrane. Thus, within such membranes, steep redox and pH gradients would bear across the nanometric platelets and separate the two counter-flowing solutions, a condition that may have led to the onset of an autotrophic metabolism through the reduction of carbon dioxide. Key Words: Dendrites—Framboids—Greigite—Hydrothermal chimneys—Mackinawite—Origin of life. Astrobiology 11, 933–950.

We describe a continuous high-pressure flow reactor designed to simulate the unforced convective interaction of hydrothermal solutions and ocean waters with submarine crust on early Earth—conditions appropriate to those that may have led to the onset of life. The experimental operating conditions are appropriate for investigating kinetic hydrothermal processes in the early history of any sizable wet, rocky planet. Beyond the description of the fabrication, we report an initial experiment that tested the design and investigated the feasibility of sulfide and silica dissolution in alkaline solution from iron sulfide and basaltic rock, and their possible subsequent transport as HS⁻ and H₂SiO²⁻₄ in hot alkaline solutions. Delivery of hydrogen sulfide and dihydrogen silicate ions would have led to the precipitation of ferrous hydroxide, hydroxysilicates, and iron sulfides as integral mineral components of an off-ridge compartmentalized hydrothermal mound in the Hadean. Such a mound could, we contend, have acted as a natural chemical and electrochemical reactor and, ultimately, as the source of all biochemistry on our planet. In the event, we show that an average of ∼1 mM/kg of both sulfide and silica were released throughout, though over 10 mM/kg of HS⁻ was recorded for ∼100 minutes in the early stages of the experiment. This alkaline effluent from the reactor was injected into a reservoir of a simulacrum of ferrous iron-bearing “Hadean Ocean” water in an experiment that demonstrated the capacity of such fluids to generate hydrothermal chimneys and a variety of contiguous inorganic microgeode precipitates bearing disseminations of discrete metal sulfides. Comparable natural composite structures may have acted as hatcheries for emergent life in the Hadean. Key Words: Hydrothermal reactor—Hydrothermal mound—Hydrothermal chimneys—Geodes—Transition-metal sulfides—Hadean Ocean. Astrobiology 10, 799–810.

Considering how biological macromolecules first evolved, probably within a marine environment, it seems likely the very earliest peptides were not encoded by nucleic acids, or at least not via the genetic code as we know it. An objective of the present work is to demonstrate that sequence-independent peptides, or peptides with variable and unreliable lengths and sequences, have the potential to perform a variety of chemically useful functions such as anion and cation binding and membrane and channel formation as well as simple types of catalysis. These functions tend to be performed with the assistance of the main chain CONH atoms rather than the more variable or limited side chain atoms of the peptides presumed to exist then.