2019
DOI: 10.1002/ange.201908272
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A Stark Contrast to Modern Earth: Phosphate Mineral Transformation and Nucleoside Phosphorylation in an Iron‐ and Cyanide‐Rich Early Earth Scenario

Abstract: Organophosphates were likely an important class of prebiotic molecules. However, their presence on the early Earth is strongly debated because the low availability of phosphate, which is generally assumed to have been sequestered in insoluble calcium and iron minerals, is widely viewed as a major barrier to organophosphate generation. Herein, we demonstrate that cyanide (an essential prebiotic precursor) and urea‐based solvents could promote nucleoside phosphorylation by transforming insoluble phosphate minera… Show more

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Cited by 12 publications
(16 citation statements)
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“…Our results indicate that high phosphate concentrations used in these reaction networks (8) plausibly occurred in carbonate-rich lake environments. Furthermore, the key cyanide component needed for this chemistry also preferentially accumulates in carbonate-rich lakes to make sodium ferrocyanide evaporites, which thermally decompose to sodium cyanide above 700°C (possibly via magmatic activity or flash heating from asteroid impacts) (42,53,61). Concentrated sulfur needed for prebiotic syntheses may also have accumulated as sulfite ions (62).…”
Section: Implications For Prebiotic Chemistrymentioning
confidence: 99%
“…Our results indicate that high phosphate concentrations used in these reaction networks (8) plausibly occurred in carbonate-rich lake environments. Furthermore, the key cyanide component needed for this chemistry also preferentially accumulates in carbonate-rich lakes to make sodium ferrocyanide evaporites, which thermally decompose to sodium cyanide above 700°C (possibly via magmatic activity or flash heating from asteroid impacts) (42,53,61). Concentrated sulfur needed for prebiotic syntheses may also have accumulated as sulfite ions (62).…”
Section: Implications For Prebiotic Chemistrymentioning
confidence: 99%
“…Water is the most-accepted, prebiotically relevant solvent for reactions on the early Earth, and would likely have made the phosphorylation of nucleosides even more challenging since phosphorylation is favored by anhydrous conditions [ 5 ]. In order to resolve this difficulty, various anhydrous or semihydrous solvents have been promoted that demonstrate efficient plausible prebiotic syntheses of nucleotides [ 9 , 10 , 11 , 12 , 13 ], including the semiaqueous eutectic solvent consisting of urea, ammonium formate, and water, which has demonstrated both solubilization of phosphate and promotion of phosphorylation [ 14 , 15 ]. The previously suggested eutectic mixtures’ availability on the early Earth is questionable [ 12 , 13 , 14 , 15 ].…”
Section: Introductionmentioning
confidence: 99%
“…Hence, the most plausible prebiotic scenarios should be water-based prebiotic reactions. Darwin’s “warm pond model” containing organics and phosphate substrates has been suggested to meet this need, which upon the removal of water by drying could keep the substrates intact and would be considered a site that would favor phosphorylation [ 16 ] and other condensation reactions [ 9 , 10 , 11 , 12 , 13 , 14 , 15 ].…”
Section: Introductionmentioning
confidence: 99%
“…This dichotomy of P-bearing minerals in vastly different silicate rocks raises an important question for planetary habitability, including that of the early earth: which mineral source of phosphorus is more important in a given environment? For instance, the felsic rocks generally have more P, and this P is associated with apatite, which may dissolve via reactions with carbonate [16] or NH 4 + and sulfate [17,18] prior to biological extraction. In contrast, if ultrama c rocks are more abundant (as suggested by the dominance of olivine in the upper mantle [19,20]), then the issue of a lower P abundance in olivine is overcome by the sheer volume of this mineral.…”
Section: Introductionmentioning
confidence: 99%
“…Phosphorus on the potentially habitable moons Europa and Enceladus is instead likely constrained by reactions of the subsurface oceans with ultrama c rock formed during accretion and differentiation [24][25][26]. Most P nutrient availability studies focus on felsic rock interactions such as dissolution [16][17][18]24], and here we have chosen to investigate the potential for P liberation from more ultrama c sources, given their volumetric abundance for both the early earth and for icy ocean moons.…”
Section: Introductionmentioning
confidence: 99%