Clathration of Volatiles in the Solar Nebula and Implications for the Origin of Titan's atmosphere

We describe a scenario of Titan's formation matching the constraints imposed by its current atmospheric composition. Assuming that the abundances of all elements, including oxygen, are solar in the outer nebula, we show that the icy planetesimals were agglomerated in the feeding zone of Saturn from a mixture of clathrates with multiple guest species, so-called stochiometric hydrates such as ammonia hydrate, and pure condensates. We also use a statistical thermodynamic approach to constrain the composition of multiple guest clathrates formed in the solar nebula. We then infer that krypton and xenon, that are expected to condense in the 20-30 K temperature range in the solar nebula, are trapped in clathrates at higher temperatures than 50 K. Once formed, these ices either were accreted by Saturn or remained embedded in its surrounding subnebula until they found their way into the regular satellites growing around Saturn. In order to explain the carbon monoxide and primordial argon deficiencies of Titan's atmosphere, we suggest that the satellite was formed from icy planetesimals initially produced in the solar nebula and that were partially devolatilized at a temperature not exceeding 50 K during their migration within Saturn's subnebula. The observed deficiencies of Titan's atmosphere in krypton and xenon could result from other processes that may have occurred both prior or after the completion of Titan. Thus, krypton and xenon may have been sequestrated in the form of XH3+ complexes in the solar nebula gas phase, causing the formation of noble gas-poor planetesimals ultimately accreted by Titan. Alternatively, krypton and xenon may have also been trapped efficiently in clathrates located on the satellite's surface or in its atmospheric haze.Comment: Accepted for publication in The Astrophysical Journa

Large Uncertainties in the Thermodynamics of Phosphorus (III) Oxide (P4_4O6_6) Have Significant Implications for Phosphorus Species in Planetary Atmospheres

Phosphorus (III) oxide (P$_4$O$_6$) has been suggested to be a major component of the gas phase phosphorus chemistry in the atmospheres of gas giant planets and of Venus. However, P$_4$O$_6$'s proposed role is based on thermodynamic modeling, itself based on values for the free energy of formation of P$_4$O$_6$ estimated from limited experimental data. Values of the standard Gibbs free energy of formation ($\Delta$Go(g)) of P$_4$O$_6$ in the literature differ by up to ~656 kJ/mol, a huge range. Depending on which value is assumed, P$_4$O$_6$ may either be the majority phosphorus species present or be completely absent from modeled atmospheres. Here, we critically review the literature thermodynamic values and compare their predictions to observed constraints on P$_4$O$_6$ geochemistry. We conclude that the widely used values from the NIST/JANAF database are almost certainly too low (predicting that P$_4$O$_6$ is more stable than is plausible). We show that, regardless of the value of $\Delta$Go(g) for P$_4$O$_6$ assumed, the formation of phosphine from P$_4$O$_6$ in the Venusian atmosphere is thermodynamically unfavorable. We conclude that there is a need for more robust data on both the thermodynamics of phosphorus chemistry for astronomical and geological modeling in general and for understanding the atmosphere of Venus and the gas giant planets in particular.Comment: Article published in ACS Earth Space Chem. https://pubs.acs.org/doi/full/10.1021/acsearthspacechem.3c0001

Phosphine Generation Pathways on Rocky Planets

The possibility of life in the venusian clouds was proposed in the 1960s, and recently this hypothesis has been revived with the potential detection of phosphine (PH3) in Venus\u27 atmosphere. These observations may have detected ∼5–20 ppb phosphine on Venus (Greaves et al., 2020), which raises questions about venusian atmospheric/geochemical processes and suggests that this phosphine could possibly be generated by biological processes. In such a claim, it is essential to understand the abiotic phosphorus chemistry that may occur under Venus-relevant conditions, particularly those processes that may result in phosphine generation. Here, we discuss two related abiotic routes for phosphine generation within the atmosphere of Venus. Based on our assessment, corrosion of large impactors as they ablate near Venus\u27 cloud layer, and the presence of reduced phosphorus compounds in the subcloud layer could result in production of phosphine and may explain the phosphine detected in Venus\u27 atmosphere or on other rocky planets. We end on a cautionary note: although there may be life in the clouds of Venus, the detection of a simple, single gas, phosphine, is likely not a decisive indicator

A primordial origin for the atmospheric methane of Saturn's moon Titan

The origin of Titan's atmospheric methane is a key issue for understanding the origin of the Saturnian satellite system. It has been proposed that serpentinization reactions in Titan's interior could lead to the formation of the observed methane. Meanwhile, alternative scenarios suggest that methane was incorporated in Titan's planetesimals before its formation. Here, we point out that serpentinization reactions in Titan's interior are not able to reproduce the deuterium over hydrogen (D/H) ratio observed at present in methane in its atmosphere, and would require a maximum D/H ratio in Titan's water ice 30% lower than the value likely acquired by the satellite during its formation, based on Cassini observations at Enceladus. Alternatively, production of methane in Titan's interior via radiolytic reactions with water can be envisaged but the associated production rates remain uncertain. On the other hand, a mechanism that easily explains the presence of large amounts of methane trapped in Titan in a way consistent with its measured atmospheric D/H ratio is its direct capture in the satellite's planetesimals at the time of their formation in the solar nebula. In this case, the mass of methane trapped in Titan's interior can be up to 1,300 times the current mass of atmospheric methane.Comment: Accepted for publication in Icaru

Prebiotic synthesis of phosphoenol pyruvate by α-phosphorylation-controlled triose glycolysis

Phosphoenol pyruvate is the highest-energy phosphate found in living organisms and is one of the most versatile molecules in metabolism. Consequently, it is an essential intermediate in a wide variety of biochemical pathways, including carbon fixation, the shikimate pathway, substrate-level phosphorylation, gluconeogenesis and glycolysis. Triose glycolysis (generation of ATP from glyceraldehyde 3-phosphate via phosphoenol pyruvate) is among the most central and highly conserved pathways in metabolism. Here, we demonstrate the efficient and robust synthesis of phosphoenol pyruvate from prebiotic nucleotide precursors, glycolaldehyde and glyceraldehyde. Furthermore, phosphoenol pyruvate is derived within an α-phosphorylation controlled reaction network that gives access to glyceric acid 2-phosphate, glyceric acid 3-phosphate, phosphoserine and pyruvate. Our results demonstrate that the key components of a core metabolic pathway central to energy transduction and amino acid, sugar, nucleotide and lipid biosyntheses can be reconstituted in high yield under mild, prebiotically plausible conditions

Phosphorus and Sulfur Cosmochemistry: Implications for the Origins of Life

Phosphorus is a key element for life. This work reviews the role of phosphorus in life. Theories on the origin of life are confounded by a lack of reactive phosphorus, and attempts to overcome the dearth of reactive phosphorus must employ unrealistic phosphorus compounds, energetic organic compounds, or unusual physical conditions.Meteoritic schreibersite provided an abundant source of reactive phosphorus for the early Earth. Water corrodes schreibersite to form a mixed valence series of phosphorus compounds. Schreibersite corrosion was studied by a variety of techniques, including NMR, MS, XRD, and EPR. Reduced phosphorus in schreibersite corrodes through release of phosphite radicals which react with other radicals to form the phosphorus compounds observed. These radicals are also capable of phosphorylating simple organic compounds to form P-C and P-O-C linkages.The meteoritic mass flux was calculated using the mass frequency distribution of several meteorite collections. Much of the meteoritic mass that falls to the Earth is composed of metallic material which supplies abundant reactive phosphorus. Meteorites are a comparatively poorer source of carbon. Craters concentrate both reduced phosphorus and organic compounds through geomorphologic processes.Phosphorus and sulfur biochemistry are intricately linked in metabolism. The cosmochemistry of sulfur was studied in depth using changing C/O ratios, sulfide formation kinetics, and gas diffusion. The results have implications for meteorites, studies of Jupiter, and of protoplanetary disks

Calling: Earth #032 - Matthew Pasek, Planetary Scientist

Matthew Matt Pasek, an Associate Professor in the USF School of Geosciences, discusses his research of the origin of life from the perspective of meteorites, phosphorus, and fulgurites (rocks created by lightning strikes). More about Matt can be found here: https://works.bepress.com/matthew-pasek/ http://hennarot.forest.usf.edu/main/depts/geosci/faculty/mpasek

A Role for Phosphorus Redox in Emerging and Modern Biochemistry

Phosphorus is a major biogeochemical element controlling growth in many ecosystems. It has presumably been an important element since the onset of life. In most chemical and biochemical considerations, phosphorus is synonymous with phosphates, a pentavalent oxidation state that includes the phosphate backbone of DNA and RNA, as well as major metabolites such as ATP. However, redox processing of phosphates to phosphites and phosphonates, and to even lower oxidation states provides a work-around to many of the problems of prebiotic chemistry, including phosphorus’s low solubility and poor reactivity. In addition, modern phosphorus cycling has increasingly identified reduced P compounds as playing a role, sometimes significant, in biogeochemical processes. This suggests that phosphorus is not redox-insensitive and reduced P compounds should be considered as part of the phosphorus biogeochemical cycle