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Primary terms
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mackinawite
The central portions of the Cu–Fe–Se phase system at temperatures from 900 to 300 °C
Fate of cobalt and nickel in mackinawite during diagenetic pyrite formation
Phase, morphology, elemental composition, and formation mechanisms of biogenic and abiogenic Fe-Cu-sulfide nanoparticles: A comparative study on their occurrences under anoxic conditions
Reaction pathways of iron-sulfide mineral formation: an in situ X-ray diffraction study
Non-destructive, multi-method, internal analysis of multiple inclusions in a single diamond: First occurrence of mackinawite (Fe,Ni) 1+x S
Metamorphic-hydrothermal Ag–pd–pt Mineralization in the Noril'sk Sulfide Ore Deposit, Siberia
Transition metal incorporation into mackinawite (tetragonal FeS)
Effects of CH 4 and CO 2 on the sulfidization of goethite and magnetite: an in situ Raman spectroscopic study in high-pressure capillary optical cells at room temperature
Crystal Structures of Sulfides and Other Chalcogenides
Electrical and Magnetic Properties of Sulfides
Spectroscopic Studies of Sulfides
Reactivity of Sulfide Mineral Surfaces
The tension between CO 2 dissolved at relatively high atmospheric pressure in the Hadean ocean, and H 2 generated as ocean water oxidized ferrous iron during convection in the oceanic crust, was resolved by the onset of life. We suggest that this chemosynthetic life emerged within hydrothermal mounds produced by alkaline solutions of moderate temperature in the relative safety of the deep ocean floor. Exothermic reaction between hydrothermal H 2 , HCOO − and CH 3 S − with CO 2 was catalyzed in inorganic membranes near the mound's surface by mackinawite (FeS) nanocrysts and “ready-made” clusters corresponding to the greigite (Fe 5 NiS 8 ) structure. Such clusters were precursors to the active centers (e.g., the C-cluster, Fe 4 NiS 5 ) of a metalloenzyme that today catalyzes acetate synthesis, viz., the bifunctional dehydrogenase enzyme (ACS/CODH). The water, and some of the acetate (H 3 C.COO − ), produced in this way were exhaled into the ocean together as fluid waste. Glycine ( + H 3 N.CH 2 .COO − ) and other amino acids, as well as tiny quantities of RNA, generated in the same milieu were trapped within tiny iron sulfide cavities. Energy from the acetate reaction, augmented by a proton gradient operating through the membrane, was spent polymerizing glycine and other amino acids into short peptides upon the phosphorylated mineral surface. In turn these peptides sequestered, and thereby protected, the catalytically and electrochemically active pyrophosphate and iron/nickel sulfide clusters, from dissolution or crystallization. Intervention of RNA as a polymerizing agent for amino acids also led to an adventitious, though crude, process of regulating metabolism—a process that was also to provide genetic information to offspring. The fluxes of energy and nutrient available in the hydrothermal mound—commensurate with the requirements of life—encouraged differentiation of the first microbes into two separate domains. At the bifurcation the Bacteria were to specialize in acetogenesis and the Archaea into methanogenesis. Representatives of both these domains left the mound by way of the ocean floor and crust to colonize the deep biosphere. Once life had emerged and evolved to the extent of being able to reduce nitrogen for use in peptides and nucleic acids, light could have been used directly as an energy source for biosynthesis. Certain bacteria may have been able to do this, where protected from hard UV by a thin coating of chemical sediment produced at a sub-aerial hot spring operating in an obducted and uplifted portion of the deep biosphere. Embedded in fresh manganiferous exhalites, early photosynthetic bacteria could further protect themselves from radiation by adsorbing manganese on the membrane. Organization of the manganese with calcium, within a membrane protein, happened to result in a CaMn 3 O 4 cluster. In Mn(IV) mode this structure could oxidize two molecules of water, evolve waste oxygen, and gain four electrons and four protons in the process to fix CO 2 for biosynthesis. All these biosynthetic pathways had probably evolved before 3.7 Ga, though the reduced nature of the planet prevented a buildup of free atmospheric oxygen until the early Proterozoic.