Three body photodissociation of the water molecule and its implications for prebiotic oxygen production

The provenance of oxygen on the Earth and other planets in the Solar System is a fundamental issue. It has been widely accepted that the only prebiotic pathway to produce oxygen in the Earth’s primitive atmosphere was via vacuum ultraviolet (VUV) photodissociation of CO2 and subsequent two O atom recombination. Here, we provide experimental evidence of three-body dissociation (TBD) of H2O to produce O atoms in both 1D and 3P states upon VUV excitation using a tunable VUV free electron laser. Experimental results show that the TBD is the dominant pathway in the VUV H2O photochemistry at wavelengths between 90 and 107.4 nm. The relative abundance of water in the interstellar space with its exposure to the intense VUV radiation suggests that the TBD of H2O and subsequent O atom recombination should be an important prebiotic O2-production, which may need to be incorporated into interstellar photochemical models.

Conditions and extent of volatile loss from the Moon during formation of the Procellarum basin

Rocks from the lunar interior are depleted in moderately volatile elements (MVEs) compared to terrestrial rocks. Most MVEs are also enriched in their heavier isotopes compared to those in terrestrial rocks. Such elemental depletion and heavy isotope enrichments have been attributed to liquid–vapor exchange and vapor loss from the protolunar disk, incomplete accretion of MVEs during condensation of the Moon, and degassing of MVEs during lunar magma ocean crystallization. New Monte Carlo simulation results suggest that the lunar MVE depletion is consistent with evaporative loss at 1,670 ± 129 K and an oxygen fugacity +2.3 ± 2.1 log units above the fayalite-magnetite-quartz buffer. Here, we propose that these chemical and isotopic features could have resulted from the formation of the putative Procellarum basin early in the Moon’s history, during which nearside magma ocean melts would have been exposed at the surface, allowing equilibration with any primitive atmosphere together with MVE loss and isotopic fractionation.

Three-Body Photodissociation of Water Molecule: An Important Prebiotic Oxygen Source

The provenance of oxygen on the Earth and other Solar planetary bodies is a fundamental issue. It has been widely accepted that the only prebiotic pathway to produce oxygen in the Earth’s primitive atmosphere was via vacuum ultraviolet (VUV) photodissociation of CO2 and subsequent two O atom recombination. Here, we provide experimental evidence of three-body dissociation (TBD) of H2O to produce O atoms in both 1D and 3P states upon vacuum ultraviolet (VUV) excitation using the newly developed tunable VUV free electron laser. Experimental results show that the TBD is the dominant pathway in the VUV H2O photochemistry at wavelengths between 90 and 107.4 nm. The relative abundance of water in the interstellar space with its exposure to intense VUV radiation suggests that the TBD of H2O and subsequent O atoms recombination should be an important prebiotic O2-production, which may need to be incorporated into interstellar photochemical models.

Prebiotic stereoselective synthesis of purine and noncanonical pyrimidine nucleotide from nucleobases and phosphorylated carbohydrates

According to a current “RNA first” model for the origin of life, RNA emerged in some form on early Earth to become the first biopolymer to support Darwinism here. Threose nucleic acid (TNA) and other polyelectrolytes are also considered as the possible first Darwinian biopolymer(s). This model is being developed by research pursuing a “Discontinuous Synthesis Model” (DSM) for the formation of RNA and/or TNA from precursor molecules that might have been available on early Earth from prebiotic reactions, with the goal of making the model less discontinuous. In general, this is done by examining the reactivity of isolated products from proposed steps that generate those products, with increasing complexity of the reaction mixtures in the proposed mineralogical environments. Here, we report that adenine, diaminopurine, and hypoxanthine nucleoside phosphates and a noncanonical pyrimidine nucleoside (zebularine) phosphate can be formed from the direct coupling reaction of cyclic carbohydrate phosphates with the free nucleobases. The reaction is stereoselective, giving only the β-anomer of the nucleotides within detectable limits. For purines, the coupling is also regioselective, giving the N-9 nucleotide for adenine as a major product. In the DSM, phosphorylated carbohydrates are presumed to have been available via reactions explored previously [Krishnamurthy R, Guntha S, Eschenmoser A (2000) Angew Chem Int Ed 39:2281–2285], while nucleobases are presumed to have been available from hydrogen cyanide and other nitrogenous species formed in Earth’s primitive atmosphere.

Cometary impacts into ocean: Thermodynamical equilibrium calculations of high-temperature O2 generation on the early Earth

The early Earth?s atmosphere apparently differed from the present atmosphere mainly in its lack of free O2, and this absence is believed to have been indispensable for the origin of early anaerobic life forms. One of the central problems in Earth science is to explain the apparent transition from the primitive atmosphere (free of O2) to the present atmosphere which contains 21% of the gas. Theoretical models suggest that the initial form of O2 in the Earth?s atmosphere may have been H2O, which was converted into atmospheric O2 mainly through photosynthesis. We have investigated an alternative (abiotic) method for the conversion of H2O to O2: a high-temperature shock generated during a cometary impact into an ocean (or on land). The calculations presented here show that 1% of the present level of O2 could have resulted from an icy 1.3x1016 kg comet entering the early (pre-oxygenic) Earth with a velocity of between about 11 and 30 km s-1.