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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.

Isotopologue ratios are anticipated to be one of the most promising signs of life that can be observed remotely. On Earth, carbon isotopes have been used for decades as evidence of modern and early metabolic processes. In fact, carbon isotopes may be the oldest evidence for life on Earth, though there are alternative geological processes that can lead to the same magnitude of fractionation. However, using isotopologues as biosignature gases in exoplanet atmospheres presents several challenges. Most significantly, we will only have limited knowledge of the underlying abiotic carbon reservoir of an exoplanet. Atmospheric carbon isotope ratios will thus have to be compared against the local interstellar medium or, better yet, their host star. A further substantial complication is the limited precision of remote atmospheric measurements using spectroscopy. The various metabolic processes that cause isotope fractionation cause less fractionation than anticipated measurement precision (biological fractionation is typically 2 to 7%). While this level of precision is easily reachable in the laboratory or with special in situ instruments, it is out of reach of current telescope technology to measure isotope ratios for terrestrial exoplanet atmospheres. Thus, gas isotopologues are poor biosignatures for exoplanets given our current and foreseeable technological limitations.

For over half a century, scientists have contemplated the potential existence of life within the clouds of Venus. Unknown chemistry leaves open the possibility that certain regions of the Venusian atmosphere are habitable. In situ atmospheric measurements with a suite of modern instruments can determine whether the cloud decks possess the characteristics needed to support life as we know it. The key habitability factors are cloud particle droplet acidity and cloud-layer water content. We envision an instrument suite to measure not only the acidity and water content of the droplets (and their variability) but additionally to confirm the presence of metals and other non-volatile elements required for life’s metabolism, verify the existence of organic material, and search for biosignature gases as signs of life. We present an astrobiology-focused mission, science goals, and instruments that can be used on both a large atmospheric probe with a parachute lasting about one hour in the cloud layers (40 to 60 km) or a fixed-altitude balloon operating at about 52 km above the surface. The latter relies on four deployable mini probes to measure habitability conditions in the lower cloud region. The mission doubles as a preparation for sample return by determining whether a subset of cloud particles is non-liquid as well as characterizing the heterogeneity of the cloud particles, thereby informing sample collection and storage methods for a return journey to Earth.

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 composition, sizes and shapes of particles in the clouds of Venus have previously been studied with a variety of in situ and remote sensor measurements. A number of major questions remain unresolved, however, motivating the development of an exploratory mission that will drop a small probe, instrumented with a single-particle autofluorescence nephelometer (AFN), into Venus’s atmosphere. The AFN is specifically designed to address uncertainties associated with the asphericity and complex refractive indices of cloud particles. The AFN projects a collimated, focused, linearly polarized, 440 nm wavelength laser beam through a window of the capsule into the airstream and measures the polarized components of some of the light that is scattered by individual particles that pass through the laser beam. The AFN also measures fluorescence from those particles that contain material that fluoresce when excited at a wavelength of 440 nm and emit at 470–520 nm. Fluorescence is expected from some organic molecules if present in the particles. AFN measurements during probe passage through the Venus clouds are intended to provide constraints on particle number concentration, size, shape, and composition. Hypothesized organics, if present in Venus aerosols, may be detected by the AFN as a precursor to precise identification via future missions. The AFN has been chosen as the primary science instrument for the upcoming Rocket Lab mission to Venus, to search for organic molecules in the cloud particles and constrain the particle composition.

Regular, low-cost Decadal-class science missions to planetary destinations will be enabled by high-ΔV small spacecraft, such as the high-energy Photon, and small launch vehicles, such as Electron, to support expanding opportunities for scientists and to increase the rate of science return. The Rocket Lab mission to Venus is a small direct entry probe planned for baseline launch in May 2023 with accommodation for a single ~1 kg instrument. A backup launch window is available in January 2025. The probe mission will spend about 5 min in the Venus cloud layers at 48–60 km altitude above the surface and collect in situ measurements. We have chosen a low-mass, low-cost autofluorescing nephelometer to search for organic molecules in the cloud particles and constrain the particle composition.

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.

Mounting evidence of chemical disequilibria in the Venusian atmosphere has heightened interest in the search for life within the planet’s cloud decks. Balloon systems are currently considered to be the superior class of aerial platform for extended atmospheric sampling within the clouds, providing the highest ratio of science return to risk. Balloon-based aerial platform designs depend heavily on payload mass and target altitudes. We present options for constant- and variable-altitude balloon systems designed to carry out science operations inside the Venusian cloud decks. The Venus Life Finder (VLF) mission study proposes a series of missions that require extended in situ analysis of Venus cloud material. We provide an overview of a representative mission architecture, as well as gondola designs to accommodate a VLF instrument suite. Current architecture asserts a launch date of 30 July 2026, which would place an orbiter and entry vehicle at Venus as early as November 29 of that same year.

Venus is known for its extreme surface temperature and its sulfuric acid clouds. But the cloud layers on Venus have similar temperature and pressure conditions to those on the surface of Earth and are conjectured to be a possible habitat for microscopic life forms. We propose a mission concept to explore the clouds of Venus for up to 30 days to evaluate habitability and search for signs of life. The baseline mission targets a 2026 launch opportunity. A super-pressure variable float altitude balloon aerobot cycles between the altitudes of 48 and 60 km, i.e., primarily traversing the lower, middle, and part of the upper cloud layers. The instrument suite is carried by a gondola design derived from the Pioneer Venus Large Probe pressure vessel. The aerobot transmits data via an orbiter relay combined with a direct-to-Earth link. The orbiter is captured into a 6-h retrograde orbit with a low, roughly 170-degree, inclination. The total mass of the orbiter and entry probe is estimated to be 640 kg. An alternate concept for a constant float altitude balloon is also discussed as a lower complexity option compared to the variable float altitude version. The proposed mission would complement other planned missions and could help elucidate the limits of habitability and the role of unknown chemistry or possibly life itself in the Venus atmosphere.

Finding evidence of extraterrestrial life would be one of the most profound scientific discoveries ever made, advancing humanity into a new epoch of cosmic awareness. The Venus Life Finder (VLF) missions feature a series of three direct atmospheric probes designed to assess the habitability of the Venusian clouds and search for signs of life and life itself. The VLF missions are an astrobiology-focused set of missions, and the first two out of three can be launched quickly and at a relatively low cost. The mission concepts come out of an 18-month study by an MIT-led worldwide consortium.

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.

The search for signs of life through the detection of exoplanet atmosphere biosignature gases is gaining momentum. Yet, only a handful of rocky exoplanet atmospheres are suitable for observation with planned next-generation telescopes. To broaden prospects, we describe the possibilities for an aerial, liquid water cloud-based biosphere in the atmospheres of sub Neptune-sized temperate exoplanets, those receiving Earth-like irradiation from their host stars. One such planet is known (K2-18b) and other candidates are being followed up. Sub Neptunes are common and easier to study observationally than rocky exoplanets because of their larger sizes, lower densities, and extended atmospheres or envelopes. Yet, sub Neptunes lack any solid surface as we know it, so it is worthwhile considering whether their atmospheres can support an aerial biosphere. We review, synthesize, and build upon existing research. Passive microbial-like life particles must persist aloft in a region with liquid water clouds for long enough to metabolize, reproduce, and spread before downward transport to lower altitudes that may be too hot for life of any kind to survive. Dynamical studies are needed to flesh out quantitative details of life particle residence times. A sub Neptune would need to be a part of a planetary system with an unstable asteroid belt in order for meteoritic material to provide nutrients, though life would also need to efficiently reuse and recycle metals. The origin of life may be the most severe limiting challenge. Regardless of the uncertainties, we can keep an open mind to the search for biosignature gases as a part of general observational studies of sub Neptune exoplanets.

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.

Despite more than one hundred years of work on organosilicon chemistry, the basis for the plausibility of silicon-based life has never been systematically addressed nor objectively reviewed. We provide a comprehensive assessment of the possibility of silicon-based biochemistry, based on a review of what is known and what has been modeled, even including speculative work. We assess whether or not silicon chemistry meets the requirements for chemical diversity and reactivity as compared to carbon. To expand the possibility of plausible silicon biochemistry, we explore silicon’s chemical complexity in diverse solvents found in planetary environments, including water, cryosolvents, and sulfuric acid. In no environment is a life based primarily around silicon chemistry a plausible option. We find that in a water-rich environment silicon’s chemical capacity is highly limited due to ubiquitous silica formation; silicon can likely only be used as a rare and specialized heteroatom. Cryosolvents (e.g., liquid N2) provide extremely low solubility of all molecules, including organosilicons. Sulfuric acid, surprisingly, appears to be able to support a much larger diversity of organosilicon chemistry than water.

The diversity of extrasolar planets discovered in the last decade shows that we should not be constrained to look for life in environments similar to early or present-day Earth. Super-Earth exoplanets are being discovered with increasing frequency, and some will be able to retain a stable, hydrogen-dominated atmosphere. We explore the possibilities for photosynthesis on a rocky planet with a thin H2-dominated atmosphere. If a rocky, H2-dominated planet harbors life, then that life is likely to convert atmospheric carbon into methane. Outgassing may also build an atmosphere in which methane is the principal carbon species. We describe the possible chemical routes for photosynthesis starting from methane and show that less energy and lower energy photons could drive CH4-based photosynthesis as compared with CO2-based photosynthesis. We find that a by-product biosignature gas is likely to be H2, which is not distinct from the hydrogen already present in the environment. Ammonia is a potential biosignature gas of hydrogenic photosynthesis that is unlikely to be generated abiologically. We suggest that the evolution of methane-based photosynthesis is at least as likely as the evolution of anoxygenic photosynthesis on Earth and may support the evolution of complex life.

Phosphorous-containing molecules are essential constituents of all living cells. While the phosphate functional group is very common in small molecule natural products, nucleic acids, and as chemical modification in protein and peptides, phosphorous can form P–N (phosphoramidate), P–S (phosphorothioate), and P–C (e.g., phosphonate and phosphinate) linkages. While rare, these moieties play critical roles in many processes and in all forms of life. In this review we thoroughly categorize P–N, P–S, and P–C natural organophosphorus compounds. Information on biological source, biological activity, and biosynthesis is included, if known. This review also summarizes the role of phosphorylation on unusual amino acids in proteins (N- and S-phosphorylation) and reviews the natural phosphorothioate (P–S) and phosphoramidate (P–N) modifications of DNA and nucleotides with an emphasis on their role in the metabolism of the cell. We challenge the commonly held notion that nonphosphate organophosphorus functional groups are an oddity of biochemistry, with no central role in the metabolism of the cell. We postulate that the extent of utilization of some phosphorus groups by life, especially those containing P–N bonds, is likely severely underestimated and has been largely overlooked, mainly due to the technological limitations in their detection and analysis.