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Abstract Recent renewed interest in the possibility of life in the acidic clouds of Venus has led to new studies on organic chemistry in concentrated sulfuric acid. We have previously found that the majority of amino acids are stable in the range of Venus’ cloud sulfuric acid concentrations (81% and 98% w/w, the rest being water). The natural next question is whether dipeptides, as precursors to larger peptides and proteins, could be stable in this environment. We investigated the reactivity of the peptide bond using 20 homodipeptides and find that the majority of them undergo solvolysis within a few weeks, at both sulfuric acid concentrations. Notably, a few exceptions exist. HH and GG dipeptides are stable in 98% w/w sulfuric acid for at least 4 months, while II, LL, VV, PP, RR and KK resist hydrolysis in 81% w/w sulfuric acid for at least 5 weeks. Moreover, the breakdown process of the dipeptides studied in 98% w/w concentrated sulfuric acid is different from the standard acid-catalyzed hydrolysis that releases monomeric amino acids. Despite a few exceptions at a single concentration, no homodipeptides have demonstrated stability across both acid concentrations studied. This indicates that any hypothetical life on Venus would likely require a functional substitute for the peptide bond that can maintain stability throughout the range of sulfuric acid concentrations present.

Abstract Life on Earth is known to rarely make fluorinated carbon compounds, as compared to other halocarbons. We quantify this rarity, based on our exhaustive natural products database curated from available literature. We build on explanations for the scarcity of fluorine chemistry in life on Earth, namely that the exclusion of the C–F bond stems from the unique physico-chemical properties of fluorine, predominantly its extreme electronegativity and strong hydration shell. We further show that the C–F bond is very hard to synthesize and when it is made by life its potential biological functions can be readily provided by alternative functional groups that are much less costly to incorporate into existing biochemistry. As a result, the overall evolutionary cost-to-benefit balance of incorporation of the C–F bond into the chemical repertoire of life is not favorable. We argue that the limitations of organofluorine chemistry are likely universal in that they do not exclusively apply to specifics of Earth’s biochemistry. C–F bonds, therefore, will be rare in life beyond Earth no matter its chemical makeup.

The tentative detection of ppb levels of phosphine (PH3) in the clouds of Venus was extremely surprising, as this reduced gas was not expected to be a component of Venus’ oxidized atmosphere. Despite potential confirmation in legacy Pioneer Venus mass spectrometry data, the detection remains controversial. Here we review the potential production of phosphine by gas reactions, surface and sub-surface geochemistry, photochemistry, and other nonequilibrium processes. None of these potential phosphine production pathways is sufficient to explain the presence of phosphine in Venus atmosphere at near the observed abundance. 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 a strictly aerial microbial biosphere produces PH3. The detection of phosphine adds to the complexity of chemical processes in the Venusian environment and motivates better quantitation of the gas phase chemistry of phosphorus species and in situ follow-up sampling missions to Venus.

Abstract 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.

We show that the 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 for more than one year in concentrated sulfuric acid at room temperature and at acid concentrations relevant for Venus clouds (81% w/w to 98% w/w acid, the rest water). This work builds on our initial stability studies and is the first ever to test the reactivity and structural integrity of organic molecules subjected to extended incubation in concentrated sulfuric acid. The one-year-long stability of nucleic acid bases supports the notion that the Venus cloud environment—composed of concentrated sulfuric acid—may be able to support complex organic chemicals for extended periods of time.

Exploring how life is distributed in the universe is an extraordinary interdisciplinary challenge, but increasingly subject to testable hypotheses. Biology has emerged and flourished on at least one planet, and that renders the search for life elsewhere a scientific question. We cannot hope to travel to exoplanets in pursuit of other life even if we identify convincing biosignatures, but we do have direct access to planets and moons in our solar system. It is therefore a matter of deep astrobiological interest to study their histories and environments, whether or not they harbor life, and better understand the constraints that delimit the emergence and persistence of biology in any context. In this perspective, we argue that targeted chemistry- and biology-inspired experiments are informative to the development of instruments for space missions, and essential for interpreting the data they generate. This approach is especially useful for studying Venus because if it were an exoplanet we would categorize it as Earth-like based on its mass and orbital distance, but its atmosphere and surface are decidedly not Earth-like. Here, we present a general justification for exploring the solar system from an astrobiological perspective, even destinations that may not harbor life. We introduce the extreme environments of Venus, and argue that rigorous and observation-driven experiments can guide instrument development for imminent missions to the Venusian clouds. We highlight several specific examples, including the study of organic chemistry under extreme conditions, and harnessing the fluorescent properties of molecules to make a variety of otherwise challenging measurements.

The stratosphere contains haze rich in sulfuric acid, which plays a significant role in stratospheric chemistry and in global climate. Commercial aircraft deposit significant amounts of incomplete combustion products into the lower stratosphere. We have studied the stability of these incomplete combustion products to reaction with sulfuric acid, using a predictive model based on experimental reaction kinetics. We demonstrate that sulfuric acid chemistry is likely to be a significant component of the chemistry of organics in the stratosphere. We find that at least 25 of the 40 known incomplete combustion products from aviation fuel have lifetimes to reaction with aerosol sulfuric acid of at least months. We estimate that ~109 kg of long-lived products could be deposited per year in the lower stratosphere. We suggest that the high molecular weight organic compounds formed as incomplete combustion products of commercial long-haul aviation could play a significant role in the stratosphere.

The thermodynamic properties of a substance are key to predicting its behavior in physical and chemical systems. Specifically, the enthalpy of formation and entropy of a substance can be used to predict whether reactions involving that substance will proceed spontaneously under conditions of constant temperature and pressure, and if they do, what the heat and work yield of those reactions would be. Prediction of enthalpy and entropy of substances is therefore of value for substances for which those parameters have not been experimentally measured. We developed a database of 2869 experimental values of enthalpy of formation and 1403 values for entropy for substances composed of stable small molecules, derived from the literature. We developed a model for predicting enthalpy of formation and entropy from semiempirical quantum mechanical calculations of energy and atom counts, and applied the model to a comprehensive database of 16,417 small molecules. The database of small-molecule thermodynamic properties will be useful for predicting the outcome of any process that might involve the generation or destruction of volatile products, such as atmospheric chemistry, volcanism, or waste pyrolysis. Additionally, the collected experimental thermodynamic values will be of value to others developing models to predict enthalpy and entropy.

The initial reports of the presence of phosphine in the cloud decks of Venus have led to the suggestion that volcanism is 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 the interaction of explosively erupted phosphide with sulfuric acid clouds. The direct eruption of deep mantle phosphide is unphysical, but a shallower material could contain traces of phosphide, and could be erupted to the surface. The explosive eruption that efficiently transports material to the clouds would require ocean:magma interactions or the subduction of a hydrated oceanic crust, neither of which occur on modern Venus. The transport of the 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.