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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.3c00016

Hypervelocity impacts can produce features in zircon that are not normally produced by endogenic processes. However, lightning can also induce extreme pressure–temperature excursions, and itsefect on zircon has not been studied. With the aim to recognise features that form in response to extreme pressure–temperature excursions but are not unique to hypervelocity impacts, we imaged and undertook microstructural characterization of zircon in a fulgurite (a tubular body of glass andfused clasts that formed in response to a lightning strike). We document zircon with granular ZrO2 and rims of vermicular ZrO2, features which vary in abundance with increasing distance from the fulgurite’s central void. This indicates that these features formed in response to the lightning strike. Zircon dissociation to ZrO2 and SiO2 is a high-temperature, relatively low-pressure phenomenon, consistent with previous suggestions that lightning strikes involve extreme temperatures as well as pressures greater than those usually generated in Earth’s crust but rarely > 10 GPa. The rims of monoclinic ZrO2 record crystallographic evidence for precursor cubic ZrO2, demonstrating that cubic ZrO2 is not unique to hypervelocity impacts. Given the likelihood that this fulgurite experienced pressures of, at most, a few GPa, evidence for cubic ZrO2 indicates peak temperatures > 2000 °C.

Hypervelocity impacts can produce features in zircon that are not normally produced by endogenic processes. However, lightning can also induce extreme pressure–temperature excursions, and itsefect on zircon has not been studied. With the aim to recognise features that form in response to extreme pressure–temperature excursions but are not unique to hypervelocity impacts, we imaged and undertook microstructural characterization of zircon in a fulgurite (a tubular body of glass andfused clasts that formed in response to a lightning strike). We document zircon with granular ZrO2 and rims of vermicular ZrO2, features which vary in abundance with increasing distance from the fulgurite’s central void. This indicates that these features formed in response to the lightning strike. Zircon dissociation to ZrO2 and SiO2 is a high-temperature, relatively low-pressure phenomenon, consistent with previous suggestions that lightning strikes involve extreme temperatures as well as pressures greater than those usually generated in Earth’s crust but rarely > 10 GPa. The rims of monoclinic ZrO2 record crystallographic evidence for precursor cubic ZrO2, demonstrating that cubic ZrO2 is not unique to hypervelocity impacts. Given the likelihood that this fulgurite experienced pressures of, at most, a few GPa, evidence for cubic ZrO2 indicates peak temperatures > 2000 °C.

The widespread presence of ribonucleic acid (RNA) catalysts and cofactors in Earth's biosphere today suggests that RNA was the first biopolymer to support Darwinian evolution. However, most "path-hypotheses" to generate building blocks for RNA require reduced nitrogen-containing compounds not made in useful amounts in the CO2-N2-H2O atmospheres of the Hadean. We review models for Earth's impact history that invoke a single ~10^23 kg impactor (Moneta) to account for measured amounts of platinum, gold, and other siderophilic ("iron-loving") elements on the Earth and Moon. If it were the last sterilizing impactor, Moneta would have reduced the atmosphere but not its mantle, opening a "window of opportunity" for RNA synthesis, a period when RNA precursors rained from the atmosphere to land holding oxidized minerals that stabilize advanced RNA precursors and RNA. Surprisingly, this combination of physics, geology, and chemistry suggests a time when RNA formation was most probable, ~120 +/- 100 million years after Moneta's impact, or ~4.36 +/- 0.1 billion years ago. Uncertainties in this time are driven by uncertainties in rates of productive atmosphere loss and amounts of sub-aerial land., Comment: Paper accepted to ChemSystemsChem [https://onlinelibrary.wiley.com/journal/25704206] August 22, 2019

The widespread presence of ribonucleic acid (RNA) catalysts and cofactors in Earth's biosphere today suggests that RNA was the first biopolymer to support Darwinian evolution. However, most "path-hypotheses" to generate building blocks for RNA require reduced nitrogen-containing compounds not made in useful amounts in the CO2-N2-H2O atmospheres of the Hadean. We review models for Earth's impact history that invoke a single ~10^23 kg impactor (Moneta) to account for measured amounts of platinum, gold, and other siderophilic ("iron-loving") elements on the Earth and Moon. If it were the last sterilizing impactor, Moneta would have reduced the atmosphere but not its mantle, opening a "window of opportunity" for RNA synthesis, a period when RNA precursors rained from the atmosphere to land holding oxidized minerals that stabilize advanced RNA precursors and RNA. Surprisingly, this combination of physics, geology, and chemistry suggests a time when RNA formation was most probable, ~120 +/- 100 million years after Moneta's impact, or ~4.36 +/- 0.1 billion years ago. Uncertainties in this time are driven by uncertainties in rates of productive atmosphere loss and amounts of sub-aerial land., Comment: Paper accepted to ChemSystemsChem [https://onlinelibrary.wiley.com/journal/25704206] August 22, 2019

Motivated by the possibility of comparing theoretical predictions of Lake Vostok's composition with future in situ measurements, we investigate the composition of clathrates that are expected to form in this environment from the air supplied to the lake by melting ice. In order to establish the best possible correlation between the lake water composition with that of air clathrates formed in situ, we use a statistical thermodynamic model based on the description of the guest-clathrate interaction by a spherically averaged Kihara potential with a nominal set of potential parameters. We determine the fugacities of the different volatiles present in the lake by defining a "pseudo" pure substance dissolved in water owning the average properties of the mixture and by using the Redlich-Kwong equation of state to mimic its thermodynamic behavior. Irrespective of the clathrate structure considered in our model, we find that xenon and krypton are strongly impoverished in the lake water (a ratio in the 0.04--0.1 range for xenon and a ratio in the $\sim$0.15--0.3 range for krypton), compared to their atmospheric abundances. Argon and methane are also found depleted in the Lake Vostok water by factors in the 0.5--0.95 and 0.3--0.5 ranges respectively, compared to their atmospheric abundances. On the other hand, the carbone dioxide abundance is found substantially enriched in the lake water compared to its atmospheric abundance (by a factor in the 1.6--5 range at 200 residence times). The comparison of our predictions of the CO$_2$ and CH$_4$ mole fractions in Lake Vostok with future in situ measurements will allow disentangling between the possible supply sources., Comment: Accepted for publication in Astrobiology

Motivated by the possibility of comparing theoretical predictions of Lake Vostok's composition with future in situ measurements, we investigate the composition of clathrates that are expected to form in this environment from the air supplied to the lake by melting ice. In order to establish the best possible correlation between the lake water composition with that of air clathrates formed in situ, we use a statistical thermodynamic model based on the description of the guest-clathrate interaction by a spherically averaged Kihara potential with a nominal set of potential parameters. We determine the fugacities of the different volatiles present in the lake by defining a "pseudo" pure substance dissolved in water owning the average properties of the mixture and by using the Redlich-Kwong equation of state to mimic its thermodynamic behavior. Irrespective of the clathrate structure considered in our model, we find that xenon and krypton are strongly impoverished in the lake water (a ratio in the 0.04--0.1 range for xenon and a ratio in the $\sim$0.15--0.3 range for krypton), compared to their atmospheric abundances. Argon and methane are also found depleted in the Lake Vostok water by factors in the 0.5--0.95 and 0.3--0.5 ranges respectively, compared to their atmospheric abundances. On the other hand, the carbone dioxide abundance is found substantially enriched in the lake water compared to its atmospheric abundance (by a factor in the 1.6--5 range at 200 residence times). The comparison of our predictions of the CO$_2$ and CH$_4$ mole fractions in Lake Vostok with future in situ measurements will allow disentangling between the possible supply sources., Comment: Accepted for publication in Astrobiology

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 Icarus

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 Icarus

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 Journal

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 Journal

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.