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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

Measurements of trace gases in planetary atmospheres help us explore chemical conditions different to those on Earth. Our nearest neighbour, Venus, has cloud decks that are temperate but hyperacidic. Here we report the apparent presence of phosphine (PH3) gas in Venus’s atmosphere, where any phosphorus should be in oxidized forms. Single-line millimetre-waveband spectral detections (quality up to ~15σ) from the JCMT and ALMA telescopes have no other plausible identification. Atmospheric PH3 at ~20 ppb abundance is inferred. The presence of PH3 is unexplained after exhaustive study of steady-state chemistry and photochemical pathways, with no currently known abiotic production routes in Venus’s atmosphere, clouds, surface and subsurface, or from lightning, volcanic or meteoritic delivery. PH3 could originate from unknown photochemistry or geochemistry, or, by analogy with biological production of PH3 on Earth, from the presence of life. Other PH3 spectral features should be sought, while in situ cloud and surface sampling could examine sources of this gas. The detection of ~20 ppb of phosphine in Venus clouds by observations in the millimetre-wavelength range from JCMT and ALMA is puzzling, because according to our knowledge of Venus, no phosphine should be there. As the most plausible formation paths do not work, the source could be unknown chemical processes—maybe even life?

A long-term goal of exoplanet studies is the identification and detection of biosignature gases. Beyond the most discussed biosignature gas O$_2$, only a handful of gases have been considered in detail. Here we evaluate phosphine (PH$_3$). On Earth, PH$_3$ is associated with anaerobic ecosystems, and as such is a potential biosignature gas on anoxic exoplanets. We simulate CO$_2-$ and H$_2-$dominated habitable terrestrial planet atmospheres. We find that PH$_3$ can accumulate to detectable concentrations on planets with surface production fluxes of 10$^{10}$-10$^{14}$ cm$^{-2}$ s$^{-1}$ (corresponding to surface concentrations of 10s of ppb to 100s of ppm), depending on atmospheric composition and UV flux. While high, such surface fluxes are comparable to the global terrestrial production rate of CH$_4$ (10$^{11}$ cm$^{-2}$ s$^{-1}$) and below the maximum local terrestrial PH$_3$ production rate (10$^{14}$ cm$^{-2}$ s$^{-1}$). As with other gases, PH$_3$ can more readily accumulate on low-UV planets, e.g. planets orbiting quiet M-dwarfs or with a photochemical UV shield. If detected, PH$_3$ is a promising biosignature gas, as it has no known abiotic false positives on terrestrial planets that could generate the high fluxes required for detection. PH$_3$ also has 3 strong spectral features such that in any atmosphere scenario 1 of the 3 will be unique compared to other dominant spectroscopic molecules. PH$_3$'s weakness as a biosignature gas is its high reactivity, requiring high outgassing for detectability. We calculate that 10s of hours of JWST time are required for a potential detection of PH$_3$. Yet because PH$_3$ is spectrally active in the same wavelength regions as other atmospherically important molecules (e.g., H$_2$O and CH$_4$), searches for PH$_3$ can be carried out at no additional observational cost to searches for other molecules relevant to exoplanet habitability., Accepted to Astrobiology. Expected publication info: Volume 20, Issue 2

Significance This research provides a transformative hypothesis for the chemistry of the atmospheric cloud layers of Venus while reconciling decades-long atmosphere anomalies. Our model predicts that the clouds are not entirely made of sulfuric acid, but are partially composed of ammonium salt slurries, which may be the result of biological production of ammonia in cloud droplets. As a result, the clouds are no more acidic than some extreme terrestrial environments that harbor life. Life could be making its own environment on Venus. The model’s predictions for the abundance of gases in Venus’ atmosphere match observation better than any previous model, and are readily testable., 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 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 semisolid ammonium salt slurries, with a pH of ∼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.

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., A short overview of the Venusian PH3 discovery and the scientific debate that arose since the original candidate detection in September 2020. Additional discussion of possible non-canonical sources of PH3 on Venus is also included. arXiv admin note: text overlap with arXiv:2009.06499

Phosphorus is an essential element for all life on Earth, yet trivalent phosphorus (e.g., in phosphines) appears to be almost completely absent from biology. Instead phosphorus is utilized by life almost exclusively as phosphate, apart from a small contingent of other pentavalent phosphorus compounds containing structurally similar chemical groups. In this work, we address four previously stated arguments as to why life does not explore trivalent phosphorus: (1) precedent (lack of confirmed instances of trivalent phosphorus in biochemicals suggests that life does not have the means to exploit this chemistry), (2) thermodynamic limitations (synthesizing trivalent phosphorus compounds is too energetically costly), (3) stability (phosphines are too reactive and readily oxidize in an oxygen (O2)-rich atmosphere), and (4) toxicity (the trivalent phosphorus compounds are broadly toxic). We argue that the first two of these arguments are invalid, and the third and fourth arguments only apply to the O2-rich environment of modern Earth. Specifically, both the reactivity and toxicity of phosphines are specific to aerobic life and strictly dependent on O2-rich environment. We postulate that anaerobic life persisting in anoxic (O2-free) environments may exploit trivalent phosphorus chemistry much more extensively. We review the production of trivalent phosphorus compounds by anaerobic organisms, including phosphine gas and an alkyl phosphine, phospholane. We suggest that the failure to find more such compounds in modern terrestrial life may be a result of the strong bias of the search for natural products toward aerobic organisms. We postulate that a more thorough identification of metabolites of the anaerobic biosphere could reveal many more trivalent phosphorus compounds. We conclude with a discussion of the implications of our work for the origin and early evolution of life, and suggest that trivalent phosphorus compounds could be valuable markers for both extraterrestrial life and the Shadow Biosphere on Earth.

We present a model of the evolution of control systems in a genome under environmental constraints. The model conceptually follows the Jacob and Monod model of gene control. Genes contain control elements which respond to the internal state of the cell as well as the environment to control expression of a coding region. Control and coding regions evolve to maximize a fitness function between expressed coding sequences and the environment. 118 runs of the model run to an average of 1.4 x 10^6 `generations' each with a range of starting parameters probed the conditions under which genomes evolved a `default style' of control. Unexpectedly, the control logic that evolved was not significantly correlated to the complexity of the environment. Genetic logic was strongly correlated with genome complexity and with the fraction of genes active in the cell at any one time. More complex genomes correlated with the evolution of genetic controls in which genes were active (`default on'), and a low fraction of genes being expressed correlated with a genetic logic in which genes were biased to being inactive unless positively activated (`default off' logic). We discuss how this might relate to the evolution of the complex eukaryotic genome, which operates in a `default off' mode., 25 pages, 8 figures, 1 table

The chemistry of life requires a solvent, which for life on Earth is water. Several alternative solvents have been suggested, but there is little quantitative analysis of their suitability as solvents for life. To support a novel (non-terrestrial) biochemistry, a solvent must be able to form a stable solution of a diverse set of small molecules and polymers, but must not dissolve all molecules. Here, we analyze the potential of concentrated sulfuric acid (CSA) as a solvent for biochemistry. As CSA is a highly effective solvent but a reactive substance, we focused our analysis on the stability of chemicals in sulfuric acid, using a model built from a database of kinetics of reaction of molecules with CSA. We consider the sulfuric acid clouds of Venus as a test case for this approach. The large majority of terrestrial biochemicals have half-lives of less than a second at any altitude in Venus’s clouds, but three sets of human-synthesized chemicals are more stable, with average half-lives of days to weeks at the conditions around 60 km altitude on Venus. We show that sufficient chemical structural and functional diversity may be available among those stable chemicals for life that uses concentrated sulfuric acid as a solvent to be plausible. However, analysis of meteoritic chemicals and possible abiotic synthetic paths suggests that postulated paths to the origin of life on Earth are unlikely to operate in CSA. We conclude that, contrary to expectation, sulfuric acid is an interesting candidate solvent for life, but further work is needed to identify a plausible route for life to originate in it.

We describe a dataset of the quantitative reactivity of organic chemicals with concentrated sulfuric acid. As well as being a key industrial chemical, sulfuric acid is of environmental and planetary importance. In the absence of measured reaction kinetics, the reaction rate of a chemical with sulfuric acid can be estimated from the reaction rate of structurally related chemicals. To allow an approximate prediction, we have collected 589 sets of kinetic data on the reaction of organic chemicals with sulfuric acid from 262 literature sources and used a functional group-based approach to build a model of how the functional groups would react in any sulfuric acid concentration from 60–100%, and between −20 °C and 100 °C. The data set provides the original reference data and kinetic measurements, parameters, intermediate computation steps, and a set of first-order rate constants for the functional groups across the range of conditions −20 °C–100 °C and 60–100% sulfuric acid. The dataset will be useful for a range of studies in chemistry and atmospheric sciences where the reaction rate of a chemical with sulfuric acid is needed but has not been measured.

Research for possible biosignature gases on habitable exoplanet atmosphere is accelerating. We add isoprene, C5H8, to the roster of biosignature gases. We found that formation of isoprene geochemical formation is highly thermodynamically disfavored and has no known abiotic false positives. The isoprene production rate on Earth rivals that of methane (~ 500 Tg yr-1). On Earth, isoprene is rapidly destroyed by oxygen-containing radicals, but its production is ubiquitous to a diverse array of evolutionarily distant organisms, from bacteria to plants and animals-few, if any at all, volatile secondary metabolite has a larger evolutionary reach. While non-photochemical sinks of isoprene may exist, the destruction of isoprene in an anoxic atmosphere is mainly driven by photochemistry. Motivated by the concept that isoprene might accumulate in anoxic environments, we model the photochemistry and spectroscopic detection of isoprene in habitable temperature, rocky exoplanet anoxic atmospheres with a variety of atmosphere compositions under different host star UV fluxes. Limited by an assumed 10 ppm instrument noise floor, habitable atmosphere characterization using JWST is only achievable with transit signal similar or larger than that for a super-Earth sized exoplanet transiting an M dwarf star with an H2-dominated atmosphere. Unfortunately, isoprene cannot accumulate to detectable abundance without entering a run-away phase, which occurs at a very high production rate, ~ 100 times Earth's production rate. In this run-away scenario isoprene will accumulate to > 100 ppm and its spectral features are detectable with ~ 20 JWST transits. One caveat is that some spectral features are hard to be distinguished from that of methane. Despite these challenges, isoprene is worth adding to the menu of potential biosignature gases., 62 pages, 24 figures

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., v2 is in press in Astrobiology, Special Collection: Venus; v2 also expands on the potential of phosphides from the deep mantle volcanism as a source of PH3 (as suggested by Truong and Lunine 2021: https://www.pnas.org/content/118/29/e2021689118) and shows the volcanic source of PH3 to be unlikely

We revisit the hypothesis that there is life in the Venusian clouds to propose a life cycle that resolves the conundrum of how life can persist aloft for hundreds of millions to billions of years. Most discussions of an aerial biosphere in the Venus atmosphere temperate layers never address whether the life-small microbial-type particles-is free floating or confined to the liquid environment inside cloud droplets. We argue that life must reside inside liquid droplets such that it will be protected from a fatal net loss of liquid to the atmosphere, an unavoidable problem for any free-floating microbial life forms. However, the droplet habitat poses a lifetime limitation: Droplets inexorably grow (over a few months) to large enough sizes that are forced by gravity to settle downward to hotter, uninhabitable layers of the Venusian atmosphere. (Droplet fragmentation-which would reduce particle size-does not occur in Venusian atmosphere conditions.) We propose for the first time that the only way life can survive indefinitely is with a life cycle that involves microbial life drying out as liquid droplets evaporate during settling, with the small desiccated 'spores' halting at, and partially populating, the Venus atmosphere stagnant lower haze layer (33-48 km altitude). We, thus, call the Venusian lower haze layer a 'depot' for desiccated microbial life. The spores eventually return to the cloud layer by upward diffusion caused by mixing induced by gravity waves, act as cloud condensation nuclei, and rehydrate for a continued life cycle. We also review the challenges for life in the extremely harsh conditions of the Venusian atmosphere, refuting the notion that the 'habitable' cloud layer has an analogy in any terrestrial environment., Open Access Astrobiology Article

Finding life on exoplanets from telescopic observations is an ultimate goal of exoplanet science. Life produces gases and other substances, such as pigments, which can have distinct spectral or photometric signatures. Whether or not life is found with future data must be expressed with probabilities, requiring a framework of biosignature assessment. We present a framework in which we advocate using biogeochemical "Exo-Earth System" models to simulate potential biosignatures in spectra or photometry. Given actual observations, simulations are used to find the Bayesian likelihoods of those data occurring for scenarios with and without life. The latter includes "false positives" where abiotic sources mimic biosignatures. Prior knowledge of factors influencing planetary inhabitation, including previous observations, is combined with the likelihoods to give the Bayesian posterior probability of life existing on a given exoplanet. Four components of observation and analysis are necessary. 1) Characterization of stellar (e.g., age and spectrum) and exoplanetary system properties, including "external" exoplanet parameters (e.g., mass and radius) to determine an exoplanet's suitability for life. 2) Characterization of "internal" exoplanet parameters (e.g., climate) to evaluate habitability. 3) Assessment of potential biosignatures within the environmental context (components 1-2) and any corroborating evidence. 4) Exclusion of false positives. The resulting posterior Bayesian probabilities of life's existence map to five confidence levels, ranging from "very likely" (90-100%) to "very unlikely" ($\le$10%) inhabited., Comment: Part of a NASA Nexus for Exoplanet System Science (NExSS) series of 5 papers. V.3 published as an Open Access paper in Astrobiology

Only about 100 natural products are known to contain a nitrogen-sulfur (N-S) bond. This review thoroughly categorizes N-S bond-containing compounds by structural class. Information on biological source, biological activity, and biosynthesis is included, if known. We also review the role of N-S bond functional groups as post-translational modifications of amino acids in proteins and peptides, emphasizing their role in the metabolism of the cell.

Am Anfang dieses Buches haben wir die Idee des grosen Filters vorgestellt, etwas, das zwischen der Entstehung von Planeten (vom dem wir wissen, dass es oft passiert) und der Existenz technologischer Zivilisationen (die selten zu sein scheinen) steht. Wir haben uns gefragt, was dieser grose Filter wohl sein konnte, und vermutet, dass es sich im Laufe der rund 4 Mrd. Jahre um jeden der vielen Schritte handeln konnte, die vom Ursprung des Lebens zur modernen Menschheit gefuhrt haben.

Vermutlich wurde das Leben zu Beginn von Reaktionen zwischen chemischen Stoffen – vor allem aus Gestein und Gasen – angetrieben, die bereits in der Umgebung der jungen Erde vorhanden waren. Wenn Leben an hydrothermalen Quellen in den Tiefen der Ozeane entstanden ist, dann reagierten das vulkanische Gestein und die Gase, die von diesen Vulkanen ausgestosen wurden, wie Kohlendioxid und Wasserstoff, zu Methan und Wasser. Auch heute noch verwenden manche Mikroorganismen diese Energiequellen, doch kann sich das Leben an alle zur Verfugung stehenden Energiequellen anpassen.

Die Welt der Prokaryoten setzt sich aus Archaebakterien und Bakterien zusammen, die allein aufgrund ihrer schieren Anzahl unsere Welt beherrschen. Doch die Evolution fuhrte zu einer immer hoheren Komplexitat, und die Entstehung eines weiteren wichtigeren Zelltyps, der eukaryotischen Zelle, stellte dabei eine entscheidende Innovation dar. Zwar sind viele Eukaryoten genau wie Bakterien einzellige Organismen, doch manche Eukaryoten bildeten vielzellige Lebensformen, bei denen die Zellen einen groseren Organismus bilden, der viel mehr ist als die Ansammlung seiner Teile (mehr uber Vielzeller s. Kap. 8).

Alles Leben besteht aus Zellen. Einzellige Organismen bestehen, wie der Namen schon sagt, aus nur einer Zelle, auch wenn diese Zelle auserordentlich komplex sein kann. Vielzeller verfugen nicht nur uber viele Zellen, sondern auch zahlreiche unterschiedliche.

Wir widmen uns nun der Frage, ob ein Planet grundsatzlich Leben aufrechterhalten kann. Die Minimalvoraussetzungen fur komplexes Leben sind deutlich hoher als fur mikrobielles. Wir werden zuerst uberlegen, was unsere Erde zu einem bewohnbaren Planeten macht und inwiefern ihre Geschichte im Sonnensystem eng mit dem Auftauchen und dem Fortbestand von Leben zusammenhangt.

Menschen, oder zumindest die Menschen, die dieses Buch lesen, sind oft stolz auf ihre Intelligenz. Die Menschen haben die fortschrittlichste materielle Kultur und das komplizierteste und flexibelste Kommunikationssystem aller Wesen auf der Erde. Doch auch viele Tiere haben Fahigkeiten, die auf ein erhebliches Mas an Intelligenz schliesen lassen.

Wir konnen die Hypothese vom lebendigen Universum heute nicht testen, doch eines Tages werden wir so weit sein, denn wir werden immer bessere Fernerkundungen durchfuhren konnen, und vielleicht werden wir einmal geeignete Exoplaneten und Exomonde besuchen konnen. Die schlechte Nachricht ist, dass dies immer noch Jahrzehnte dauern wird, die gute, dass dies ein Forschungsprogramm ist, das Weltraumbehorden auf der ganzen Welt bereits voranbringen, etwa mit Teleskopen, die die Planeten und Monde in anderen Sonnensystemen charakterisieren. Auserdem wird die Erkundung der Planeten und Monde unseres eigenen Sonnensystems mit Teleskopen und Raumfahrzeugen wertvolle Daten liefern. Im Laufe der nachsten Jahre und Jahrzehnte wird dieser fortschreitende Marsch der Technologie immer mehr Details uber unsere kosmische Nachbarschaft enthullen. Wir sind zuversichtlich, dass, wenn Leben gefunden wird, dieses dann auf vielen Welten komplex sein wird.

Luftsauerstoff ist fur das tierische Leben unverzichtbar, vor allem fur uns selbst. Ein gesunder erwachsener Mensch kann zwei Wochen ohne Nahrung und mehrere Tage ohne Wasser aushalten, aber nicht mehr als funf Minuten ohne Sauerstoff, ohne bleibende Schaden davonzutragen. Jedes Schulkind weis, dass grune Pflanzen die Energie des Sonnenlichts nutzen, um den Sauerstoff zu erzeugen, den wir einatmen.

In diesem Buch werden wir begrunden, warum die Entwicklung komplexen Lebens in jeder stabilen Umgebung mit ausreichend Lebensraum sehr wahrscheinlich ist, sobald auf einem planetaren Korper einmal Leben entstanden ist. Das komplexe Leben auf der Erde sind die echten (obligaten) Lebensformen aus vielen Zellen, vor allem die Mitglieder aus den Reichen der Plantae (Pflanzen), Fungi (Hefen, Pilze) und Animalia (Tiere). Ihr Aufbau aus vielen spezialisierten Zellen ist das entscheidende Kennzeichen fur diese Art von weiterentwickeltem, komplexem Leben.