SearcharxivSearch

arXiv subjects

William Bains

Publications and source records attributed to William Bains.

At least 19 recordsLinked to original sources

Ionic Liquid Biospheres

Liquid is a fundamental requirement for life as we understand it, but whether that liquid has to be water is not known. We propose the hypothesis that ionic liquids (ILs) and deep eutectic solvents (DES) constitute a class of non-aqueous planetary liquids capable of persisting on a wide range of bodies where stable liquid water cannot exist. This hypothesis is motivated by key physical properties of ILs and DES. Many exhibit vapor pressures orders of magnitude lower than that of water and remain liquid across exceptionally wide temperature ranges, from cryogenic to well above terrestrial temperatures. These properties permit stable liquids to exist where liquid water would rapidly evaporate or freeze and outside of bulk phases as persistent microscale reservoirs-such as thin films and pore-filling droplets. In other words, ILs and DES can persist in environments without requiring oceans, thick atmospheres, or narrowly regulated climate conditions. We further hypothesize that ILs and DES could act as solvents for non-Earth-like life. Our hypothesis ex-tends to the idea that ILs and DES could enable prebiotic chemistry by providing long-lived, protective liquid environments for complex organic molecules on bodies such as comets and asteroids, where liquid water is absent. Based on the occurrence of DES-like mixtures as protective intracellular liquids in desiccation-tolerant plants, we propose that ILs and DES might be solvents that life elsewhere purposefully evolves. We review protein and other biomolecule studies in ILs and DES and outline planetary environments in which ILs and DES might occur by discussing available anions and cations. We present strategies to advance the IL/DES solvent hypothesis using laboratory studies, computational chemistry, planetary missions, analysis of existing spectroscopic datasets, and modeling of liquid microniches and chemical survival on small bodies.

astro-ph.EP

Warm, water-depleted rocky exoplanets with surface ionic liquids: A proposed class for planetary habitability

The discovery of thousands of exoplanets and the emergence of telescopes capable of exoplanet atmospheric characterization have intensified the search for habitable worlds. Due to selection biases, many exoplanets under study are planets deemed inhospitable because their surfaces are too warm to support liquid water. We propose that such planets could still support life through ionic liquids: Liquid salts with negligible vapor pressure that can persist on warm planets with thin atmospheres, where liquid water cannot. Ionic liquids have not previously been considered as naturally occurring substances, and thus have not been discussed in planetary science. We demonstrate in laboratory experiments that ionic liquids can form from planetary materials: Sulfuric acid combined with nitrogen-containing organic molecules. Sulfuric acid can be volcanic in origin, and organic compounds are commonly found on planetary bodies. The required planetary surface is water-depleted and must support sulfuric acid transiently in liquid phase to dissolve organics, followed by evaporation of excess liquid, conditions spanning approximately 300 K at 10^-7 atm to 350-470 K at 0.01 atm. Because ionic liquids have extremely low vapor pressures, they are not prone to evaporation, allowing small droplets or pools to persist without ocean-like reservoirs. Ionic liquids' minuscule vapor pressure at room temperature suggests possible stability on planets with negligible atmospheres, shielded by magnetic fields or rock crevices against harsh cosmic radiation. Ionic liquids can stably dissolve enzymes and other biomolecules, enabling biocatalysis and offering a plausible solvent for life, broadening the definition of habitable worlds.

astro-ph.EP

The Diversity of Exoplanetary Environments and the Search for Signs of Life Beyond Earth

Thousands of exoplanets orbit nearby stars, showcasing a remarkable diversity in mass, size, and orbits. With the James Webb Space Telescope now operational, we are observing exoplanet atmospheres and aiming to reach down to small, habitable-zone exoplanets in search of signs of habitability and possibly even biosignature gases. Given the scarcity of targets, it is imperative to embrace the known diversity and consider the range of exoplanets that might host life. We review how Earth life interacts with various atmospheric gases, noting that bacteria can survive in high concentrations of gases such as H2, He, CO2, and CO. Additionally, we consider the potential for life in alternative solvents and in cloud biospheres where rocky surfaces are excessively hot, as well as in hypothesized planetary global oceans. We highlight that life fundamentally requires metal ions for catalytic reactions, suggesting that environments without surface contact need meteoritic delivery to provide these essential elements. Despite today's observational limits, a suite of next-generation telescopes is being designed specifically for exoplanet studies, promising to expand our capabilities and understanding in the future.

astro-ph.EP

Prospects for Detecting Signs of Life on Exoplanets in the JWST Era

The search for signs of life in the Universe has entered a new phase with the advent of the James Webb Space Telescope (JWST). Detecting biosignature gases via exoplanet atmosphere transmission spectroscopy is in principle within JWST's reach. We reflect on JWST's early results in the context of the potential search for biological activity on exoplanets. The results confront us with a complex reality. Established inverse methods to interpret observed spectra-already known to be highly averaged representations of intricate 3D atmospheric processes-can lead to disparate interpretations even with JWST's quality of data. Characterizing rocky or sub-Neptune-size exoplanets with JWST is an intricate task, and moves us away from the notion of finding a definitive "silver bullet" biosignature gas. Indeed, JWST results necessitate us to allow "parallel interpretations" that will perhaps not be resolved until the next generation of observatories. Nonetheless, with a handful of habitable-zone planet atmospheres accessible given the anticipated noise floor, JWST may continue to contribute to this journey by designating a planet as biosignature gas candidate. To do this we will need to sufficiently refine our inverse methods and physical models for confidently quantifying specific gas abundances and constraining the atmosphere context. Looking ahead, future telescopes and innovative observational strategies will be essential for the reliable detection of biosignature gases.

astro-ph.EP

Simple lipids form stable higher-order structures in concentrated sulfuric acid

Venus has become a target of astrobiological interest because it is physically accessible to direct exploration, unlike exoplanets. So far this interest has been motivated not by the explicit expectation of finding life but rather by a desire to understand the limits of biology. The venusian surface is sterilizing, but the cloud deck includes regions with temperatures and pressures conventionally considered compatible with life. However, the venusian clouds are thought to consist of concentrated sulfuric acid. To determine if any fundamental features of life as we understand them here on Earth could in principle exist in these extreme solvent conditions, we tested several simple lipids for resistance to solvolysis and their ability to form structures in concentrated sulfuric acid. We find that single-chain saturated lipids with sulfate, alcohol, trimethylamine, and phosphonate head groups are resistant to sulfuric acid degradation at room temperature. Furthermore, we find that they form stable higher-order structures typically associated with lipid membranes, micelles, and vesicles. Finally, results from molecular dynamics simulations suggest a molecular explanation for the observed robustness of the lipid structures formed in concentrated sulfuric acid. We conclude with implications for the study of Venus as a target of experimental astrobiology.

physics.chem-ph

Alternative solvents for life: framework for evaluation, current status and future research

Life is a complex, dynamic chemical system that requires a dense fluid solvent in which to take place. A common assumption is that the most likely solvent for life is liquid water, and some researchers argue that water is the only plausible solvent. However, a persistent theme in astrobiological research postulates that other liquids might be cosmically common, and could be solvents for the chemistry of life. In this paper we present a new framework for the analysis of candidate solvents for life, and deploy this framework to review substances that have been suggested as solvent candidates. We categorize each solvent candidate through four criteria: occurrence, solvation, solute stability and solvent chemical functionality. Our semi-quantitative approach addresses all the requirements for a solvent not only from the point of view of its chemical properties but also from the standpoint of their biochemical function. Only the protonating solvents fulfil all the chemical requirements to be a solvent for life, and of those only water and concentrated sulfuric acid are also likely to be abundant in a rocky planetary context. Among the non-protonating solvents liquid CO2 stands out as a planetary solvent, and its potential as a solvent for life should be explored. We conclude with a discussion of whether it is possible for a biochemistry to change solvents, as an adaptation to radical changes in a planet's environment. Our analysis provides the basis for prioritizing future experimental work exploring potential complex chemistry on other planets.

astro-ph.EP

Astrobiological Potential of Venus Atmosphere Chemical Anomalies and Other Unexplained Cloud Properties

Long-standing unexplained Venus atmosphere observations and chemical anomalies point to unknown chemistry but also leave room for the possibility of life. The unexplained observations include several gases out of thermodynamic equilibrium (e.g. tens of ppm O2, the possible presence of PH3 and NH3, SO2 and H2O vertical abundance profiles), an unknown composition of large, lower cloud particles, and the "unknown absorber(s)". Here we first review relevant properties of the Venus atmosphere and then describe the atmospheric chemical anomalies and how they motivate future astrobiology missions to Venus.

astro-ph.EP

Stability of 20 Biogenic Amino Acids in Concentrated Sulfuric Acid: Implications for the Habitability of Venus' Clouds

Scientists have long speculated about the potential habitability of Venus, not at the 700K surface, but in the cloud layers located at 48-60 km altitudes, where temperatures match those found on Earth's surface. However, the prevailing belief has been that Venus' clouds cannot support life due to the cloud chemical composition of concentrated sulfuric acid-a highly aggressive solvent. In this work, we study 20 biogenic amino acids at the range of Venus' cloud sulfuric acid concentrations (81% and 98% w/w, the rest water) and temperatures. We find 19 of the biogenic amino acids we tested are either unreactive (13 in 98% w/w and 12 in 81% w/w) or chemically modified in the side chain only, after four weeks. Our major finding, therefore, is that the amino acid backbone remains intact in concentrated sulfuric acid. These findings significantly broaden the range of biologically relevant molecules that could be components of a biochemistry based on a concentrated sulfuric acid solvent.

astro-ph.EP

Fully fluorinated non-carbon compounds NF3 and SF6 as ideal technosignature gases

Waste gas products from technological civilizations may accumulate in an exoplanet atmosphere to detectable levels. We propose nitrogen trifluoride (NF3) and sulfur hexafluoride (SF6) as ideal technosignature gases. Earth life avoids producing or using any N-F or S-F bond-containing molecules and makes no fully fluorinated molecules with any element. NF3 and SF6 may be universal technosignatures owing to their special industrial properties, which unlike biosignature gases, are not species-dependent. Other key relevant qualities of NF3 and SF6 are: their extremely low water solubility, unique spectral features, and long atmospheric lifetimes. NF3 has no non-human sources and was absent from Earth's pre-industrial atmosphere. SF6 is released in only tiny amounts from fluorine-containing minerals, and is likely produced in only trivial amounts by volcanic eruptions. We propose a strategy to rule out SF6's abiotic source by simultaneous observations of SiF4, which is released by volcanoes in an order of magnitude higher abundance than SF6. Other fully fluorinated human-made molecules are of interest, but their chemical and spectral properties are unavailable. We summarize why life on Earth-and perhaps life elsewhere-avoids using F. We caution, however, that we cannot definitively disentangle an alien biochemistry byproduct from a technosignature gas.

astro-ph.EP

Stability of nucleic acid bases in concentrated sulfuric acid: Implications for the habitability of Venus' clouds

What constitutes a habitable planet is a frontier to be explored and requires pushing the boundaries of our terracentric viewpoint for what we deem to be a habitable environment. Despite Venus' 700 K surface temperature being too hot for any plausible solvent and most organic covalent chemistry, Venus' cloud-filled atmosphere layers at 48 to 60 km above the surface hold the main requirements for life: suitable temperatures for covalent bonds; an energy source (sunlight); and a liquid solvent. Yet, the Venus clouds are widely thought to be incapable of supporting life because the droplets are composed of concentrated liquid sulfuric acid-an aggressive solvent that is assumed to rapidly destroy most biochemicals of life on Earth. Recent work, however, demonstrates that a rich organic chemistry can evolve from simple precursor molecules seeded into concentrated sulfuric acid, a result that is corroborated by domain knowledge in industry that such chemistry leads to complex molecules, including aromatics. We aim to expand the set of molecules known to be stable in concentrated sulfuric acid. Here, we show that nucleic acid bases adenine, cytosine, guanine, thymine, and uracil, as well as 2,6-diaminopurine and the "core" nucleic acid bases purine and pyrimidine, are stable in sulfuric acid in the Venus cloud temperature and sulfuric acid concentration range, using UV spectroscopy and combinations of 1D and 2D 1H 13C 15N NMR spectroscopy. The stability of nucleic acid bases in concentrated sulfuric acid advances the idea that chemistry to support life may exist in the Venus cloud particle environment.

physics.chem-ph

Venus' Atmospheric Chemistry and Cloud Characteristics Are Compatible with Venusian Life

Venus is Earth's sister planet, with similar mass and density but an uninhabitably hot surface, an atmosphere with a water activity 50-100 times lower than anywhere on Earths' surface, and clouds believed to be made of concentrated sulfuric acid. These features have been taken to imply that the chances of finding life on Venus are vanishingly small, with several authors describing Venus' clouds as "uninhabitable", and that apparent signs of life there must therefore be abiotic, or artefactual. In this article, we argue that although many features of Venus can rule out the possibility that Earth life could live there, none rule out the possibility of all life based on what we know of the physical principle of life on Earth. Specifically, there is abundant energy, the energy requirements for retaining water and capturing hydrogen atoms to build biomass are not excessive, defenses against sulfuric acid are conceivable and have terrestrial precedent, and the speculative possibility that life uses concentrated sulfuric acid as a solvent instead of water remains. Metals are likely to be available in limited supply, and the radiation environment is benign. The clouds can support a biomass that could readily be detectable by future astrobiology-focused space missions from its impact on the atmosphere. Although we consider the prospects for finding life on Venus to be speculative, they are not absent. The scientific reward from finding life in such an un-Earthlike environment justifies considering how observations and missions should be designed to be capable of detecting life if it is there.

astro-ph.EP

Large Uncertainties in the Thermodynamics of Phosphorus (III) Oxide (P$_4$O$_6$) 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 ($Δ$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 $Δ$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.

astro-ph.EP

Low levels of sulphur dioxide contamination of Venusian phosphine spectra

New analysis is presented of the 1.1 mm wavelength absorption lines in Venus' atmosphere that suggested the presence of phosphine. We retrieve a sulphur dioxide observation from the JCMT archive that was simultaneous within a few days of the PH3 1-0 spectrum obtained in June 2017, and demonstrate via a radiative transfer calculation that contamination of PH3 by SO2 was ~10 per cent. We also present ALMA 2019 spectra of PH3 1-0 and an SO2 transition acquired simultaneously, and infer that SO2 line-contamination was ~2 percent (for the least-noisy half of the planetary disc). The contamination-subtracted ALMA and JCMT spectra (of 6-8 sigma confidence) are now consistent with similar absorption-depths at the two epochs. The two values span -1.9(+/-0.2) 10-4 of the continuum signal (which was re-estimated for ALMA), albeit for differing planetary areas. This suggests that the abundance attributed to phosphine in Venus' atmosphere was broadly similar in 2017 and 2019.

astro-ph.EP

Photochemical Runaway in Exoplanet Atmospheres: Implications for Biosignatures

About 2.5 billion years ago, microbes learned to harness plentiful solar energy to reduce CO$_2$ with H$_2$O, extracting energy and producing O$_2$ as waste. O$_2$ production from this metabolic process was so vigorous that it saturated its photochemical sinks, permitting it to reach "runaway" conditions and rapidly accumulate in the atmosphere despite its reactivity. Here we argue that O$_2$ may not be unique: diverse gases produced by life may experience a "runaway" effect similar to O$_2$. This runaway occurs because the ability of an atmosphere to photochemically cleanse itself of trace gases is generally finite. If produced at rates exceeding this finite limit, even reactive gases can rapidly accumulate to high concentrations and become potentially detectable. Planets orbiting smaller, cooler stars, such as the M dwarfs that are the prime targets for the James Webb Space Telescope (JWST), are especially favorable for runaway due to their lower UV emission compared to higher-mass stars. As an illustrative case study, we show that on a habitable exoplanet with an H$_2$-N$_2$ atmosphere and net surface production of NH$_3$ orbiting an M dwarf (the "Cold Haber World" scenario), the reactive biogenic gas NH$_3$ can enter runaway, whereupon an increase in the surface production flux of one order of magnitude can increase NH$_3$ concentrations by three orders of magnitude and render it detectable by JWST in just two transits. Our work on this and other gases suggests that diverse signs of life on exoplanets may be readily detectable at biochemically plausible production rates.

astro-ph.EP

Constraints on the production of phosphine by Venusian volcanoes

The initial reports of the presence of phosphine in the cloud decks of Venus has led to the suggestion that volcanism was the source of phosphine, through volcanic phosphides ejected into the clouds. Here we examine the idea that mantle plume volcanism, bringing material from the deep mantle to the surface, could generate observed amounts of phosphine through interaction of explosively erupted phosphide with sulfuric acid clouds. Direct eruption of deep mantle phosphide is unphysical, but shallower material could contain traces of phosphide, and could be erupted to the surface. Explosive eruption that efficiently transported material to the clouds would require ocean:magma interactions or subduction of hydrated oceanic crust, neither of which occur on modern Venus. The transport of erupted material to altitudes coinciding with the observations of phosphine is consequently very inefficient. Using the model proposed by Truong and Lunine as a base case, we estimate that an eruption volume of at least 21,600 km3/year would be required to explain the presence of 1 ppb phosphine in the clouds. This is greater than any historical terrestrial eruption rate, and would have several detectable consequences for remote and in situ observations to confirm. More realistic lithospheric mineralogy, volcano mechanics or atmospheric photochemistry require even more volcanism.

astro-ph.EP

Production of Ammonia Makes Venusian Clouds Habitable and Explains Observed Cloud-Level Chemical Anomalies

The atmosphere of Venus remains mysterious, with many outstanding chemical connundra. These include: the unexpected presence of ~10 ppm O2 in the cloud layers; an unknown composition of large particles in the lower cloud layers; and hard to explain measured vertical abundance profiles of SO2 and H2O. We propose a new hypothesis for the chemistry in the clouds that largely addresses all of the above anomalies. We include ammonia (NH3), a key component that has been tentatively detected both by the Venera 8 and Pioneer Venus probes. NH3 dissolves in some of the sulfuric acid cloud droplets, effectively neutralizing the acid and trapping dissolved SO2 as ammonium sulfite salts. This trapping of SO2 in the clouds together with the release of SO2 below the clouds as the droplets settle out to higher temperatures, explains the vertical SO2 abundance anomaly. A consequence of the presence of NH3 is that some Venus cloud droplets must be semi-solid ammonium salt slurries, with a pH~1, which matches Earth acidophile environments, rather than concentrated sulfuric acid. The source of NH3 is unknown, but could involve biological production; if so, then the most energy-efficient NH3-producing reaction also creates O2, explaining the detection of O2 in the cloud layers. Our model therefore predicts that the clouds are more habitable than previously thought, and may be inhabited. Unlike prior atmospheric models, ours does not require forced chemical constraints to match the data. Our hypothesis, guided by existing observations, can be tested by new Venus in situ measurements.

astro-ph.EP

Venusian phosphine: a 'Wow!' signal in chemistry?

The potential detection of ppb levels phosphine (PH3) in the clouds of Venus through millimeter-wavelength astronomical observations is extremely surprising as PH3 is an unexpected component of an oxidized environment of Venus. A thorough analysis of potential sources suggests that no known process in the consensus model of Venus' atmosphere or geology could produce PH3 at anywhere near the observed abundance. Therefore, if the presence of PH3 in Venus' atmosphere is confirmed, it is highly likely to be the result of a process not previously considered plausible for Venusian conditions. The source of atmospheric PH3 could be unknown geo- or photochemistry, which would imply that the consensus on Venus' chemistry is significantly incomplete. An even more extreme possibility is that strictly aerial microbial biosphere produces PH3. This paper summarizes the Venusian PH3 discovery and the scientific debate that arose since the original candidate detection one year ago.

astro-ph.EP

Phosphine on Venus Cannot be Explained by Conventional Processes

The recent candidate detection of ~1 ppb of phosphine in the middle atmosphere of Venus is so unexpected that it requires an exhaustive search for explanations of its origin. Phosphorus-containing species have not been modelled for Venus' atmosphere before and our work represents the first attempt to model phosphorus species in the Venusian atmosphere. We thoroughly explore the potential pathways of formation of phosphine in a Venusian environment, including in the planet's atmosphere, cloud and haze layers, surface, and subsurface. We investigate gas reactions, geochemical reactions, photochemistry, and other non-equilibrium processes. None of these potential phosphine production pathways are sufficient to explain the presence of ppb phosphine levels on Venus. If PH3's presence in Venus' atmosphere is confirmed, it therefore is highly likely to be the result of a process not previously considered plausible for Venusian conditions. The process could be unknown geochemistry, photochemistry, or even aerial microbial life, given that on Earth phosphine is exclusively associated with anthropogenic and biological sources. The detection of phosphine adds to the complexity of chemical processes in the Venusian environment and motivates in situ follow up sampling missions to Venus. Our analysis provides a template for investigation of phosphine as a biosignature on other worlds.

astro-ph.EP