We have shown that ferrous ion at neutral pH photoreduces water to hydrogen with a high quantum yield on excitation with near-ultraviolet light. This simple system also efficiently reduces carbon dioxide (bicarbonate ions) to formaldehyde. Overall, these reactions offer a solution to a dilemma confronting the standard or Oparin-Urey model of the origin oflife. If carbon dioxide was the main form ofcarbon on the primitive earth, the ferrous photoreaction would have provided the reduced carbon necessary to form amino acids and other biogenetic molecules. We believe this system may have been the progenitor to the biological photosynthetic systems.The quantum yield for the formation of hydrogen on irradiating aqueous ferrous ion at neutral pH with near-ultraviolet light is surprisingly high, >0.3 (1). A concerted reaction mechanism was proposed to explain these results. The photooxidation offerrous ion in the Archaen oceans has been proposed as an explanation of the Banded Iron Formations (2) and supporting evidence has been obtained (3-5). We were interested in the relevance of this reaction to the hypothesis that early photosynthesis could involve the formation of hydrogen (6). We have suggested (1) that this source of hydrogen may also contribute to the solution of an increasingly vexing problem concerning the origin of essential constituents for the chemical origin of life. The comprehensive data of Stribling and Miller (7) clearly show that the yield of amino acids from a spark discharge decreases continuously as the reduction level of carbon decreases from -4 (methane) through -2 (carbon monoxide) and drops to insignificance on approaching +4 (carbon dioxide). However, geochemical models increasingly favor the emission of carbon dioxide, not methane, from degassing of the early earth (8-10), although there is no geological evidence available on this important matter. A continuous and large-scale production of reducing equivalents is thus needed as an alternative standard model of the origin of life. It is possible that hydrogen formation from irradiated aqueous ferrous ion at neutral pH or, more likely, the highly reactive intermediate reducing equivalents, served to reduce the carbon dioxide. Getoff (11,12) reported that UV light induces photochemical reduction of carbon dioxide in aqueous solutions of ferrous ion leading to the formation of several organic compounds. Ackerman et al. (13) have shown that in the presence of transition metal salts aqueous saturated solutions of carbon dioxide were reduced to formate and formaldehyde and then, in low yield, to methanol and methane when irradiated with UV light of 254 nm. Joe et al.t report that formate and formaldehyde were produced on irradiating solid ferrous carbonate suspended in water. Most of the above work was exploratory and detailed yields were not measured. Our quantitative data indicate that irradiating aqueous ferrous ion at neutral pH with near-UV light (306-390 nm) reduces bicarbonate solutions to formaldehyde in good yield.
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