A Stark Contrast to Modern Earth: Phosphate Mineral Transformation and Nucleoside Phosphorylation in an Iron‐ and Cyanide‐Rich Early Earth Scenario

Burcar, Bradley T.; Castañeda, Alma D.; Lago, Jennifer; Daniel, Mischael; Pasek, Matthew A.; Hud, Nicholas V.; Orlando, Thomas M.; Menor‐Salván, César

doi:10.1002/anie.201908272

Cited by 28 publications

(25 citation statements)

References 50 publications

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“…It was pointed out previously, however, that vivianite can be solubilised by cyanide, generating ferrocyanide (Fe(CN) 6 4- ) and PO 4 3- in the process 2 , 3 – an idea recently adopted by others. 31 As hydrogen cyanide is generated by a variety of mechanisms during meteoritic impacts 32 , 33 , 34 this method of ‘rescuing’ PO 4 3- from Fe 2+ is consistent with the proposed source of PO 4 3- and our previously proposed geochemical and prebiotic scheme. 2 , 3 , 5 …”

Section: Correlation Of Experimental Results With Early Earth Environsupporting

confidence: 85%

Supply of phosphate to early Earth by photogeochemistry after meteoritic weathering

2020

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During terrestrial differentiation, the relatively small amount of phosphorus that migrated to the lithosphere was incorporated into igneous rock, predominantly in the form of basic calcium orthophosphate (Ca 10 (PO 4 ) 6 (OH,F,Cl) 2 , apatite). Yet, the highly insoluble nature of calcium apatite presents a significant problem to those contemplating the origin of life given the foundational role of phosphate (PO 4 3- ) in extant biology and the apparent requirement for PO 4 3- as a catalyst, buffer and reagent in prebiotic chemistry. Reduced meteorites such as enstatite chondrites are highly enriched in phosphide minerals, and upon reaction with water these minerals can release phosphorus species of various oxidation states. Here, we demonstrate how reduced phosphorus species can be fully oxidized to PO 4 3- simply by the action of ultraviolet light on H 2 S/HS - . We used low pressure Hg lamps to simulate UV output from the young Sun and 31 P NMR spectroscopy to monitor the progress of reactions. Our experimental findings provide a cosmochemically and geochemically plausible means for supply of PO 4 3- that was widely available to prebiotic chemistry and nascent life on early Earth, and potentially on other planets.

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Section: Correlation Of Experimental Results With Early Earth Environsupporting

confidence: 85%

Supply of phosphate to early Earth by photogeochemistry after meteoritic weathering

2020

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“…There are several Ca 2+ ‐rich early Earth minerals, which might have acted as a source. [ 27–29 ] The vesicles adhere to the substrate in a dome‐like shape. [ 30 ] Addition of chelators leads to gradual depletion of Ca 2+ from the aqueous medium including the space between the surface and the membrane, leading to the removal of pinning points.…”

Section: Discussionmentioning

confidence: 99%

Subcompartmentalization and Pseudo‐Division of Model Protocells

Spustová

Köksal

Ainla

et al. 2020

Small

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Membrane enclosed intracellular compartments have been exclusively associated with the eukaryotes, represented by the highly compartmentalized last eukaryotic common ancestor. Recent evidence showing the presence of membranous compartments with specific functions in archaea and bacteria makes it conceivable that the last universal common ancestor and its hypothetical precursor, the protocell, may have exhibited compartmentalization. To the authors’ knowledge, there are no experimental studies yet that have tested this hypothesis. They report on an autonomous subcompartmentalization mechanism for protocells which results in the transformation of initial subcompartments to daughter protocells. The process is solely determined by the fundamental materials properties and interfacial events, and does not require biological machinery or chemical energy supply. In the light of the authors’ findings, it is proposed that similar events may have taken place under early Earth conditions, leading to the development of compartmentalized cells and potentially, primitive division.

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“…The samples were monitored by 1 H NMR over this 15 day timeframe to identify the formation of 1) formamide and 2) formate, respectively. Concentrations were calculated by integration of NMR peaks, and NMR analyses procedures followed Burcar et al (2019). These systems were closed systems where water was not free to evaporate.…”

Section: B Determination Of Liquid State and Speciation Analysis Of mentioning

confidence: 99%

The Prebiotic Provenance of Semi-Aqueous Solvents

Lago

Burcar

Hud

et al. 2020

Orig Life Evol Biosph

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The numerous and varied roles of phosphorylated organic molecules in biochemistry suggest they may have been important to the origin of life. The prominence of phosphorylated molecules presents a conundrum given that phosphorylation is a thermodynamically unfavorable, endergonic process in water, and most natural sources of phosphate are poorly soluble. We recently demonstrated that a semi-aqueous solvent consisting of urea, ammonium formate, and water (UAFW) supports the dissolution of phosphate and the phosphorylation of nucleosides. However, the prebiotic feasibility and robustness of the UAFW system are unclear. Here, we study the UAFW system as a medium in which phosphate minerals are potentially solubilized. Specifically, we conduct a series of chemical experiments alongside thermodynamic models that simulate the formation of ammonium formate from the hydrolysis of hydrogen cyanide, and demonstrate the stability of formamide in such solvents (as an aqueous mixture). The dissolution of hydroxylapatite requires a liquid medium, and we investigate whether a UAFW system is solid or liquid over varied conditions, finding that this characteristic is controlled by the molar ratios of the three components. For liquid UAFW mixtures, we also find the solubility of phosphate is higher when the quantity of ammonium formate is greater than urea. We suggest the urea within the system can lower the activity of water, help create a stable and persistent solution, and may act as a condensing agent/catalyst to improve nucleoside phosphorylation yields.

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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

Cited by 28 publications

References 50 publications

Supply of phosphate to early Earth by photogeochemistry after meteoritic weathering

Supply of phosphate to early Earth by photogeochemistry after meteoritic weathering

Subcompartmentalization and Pseudo‐Division of Model Protocells

The Prebiotic Provenance of Semi-Aqueous Solvents

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