UV Transmission in Prebiotic Environments on Early Earth.

Ultraviolet (UV) light is likely to have played important roles in surficial origins of life scenarios, potentially as a productive source of energy and molecular activation, as a selective means to remove unwanted side products, or as a destructive mechanism resulting in loss of molecules/biomolecules over time. The transmission of UV light through prebiotic waters depends upon the chemical constituents of such waters, but constraints on this transmission are limited. Here, we experimentally measure the molar decadic extinction coefficients for a number of small molecules used in various prebiotic synthetic schemes. We find that many small feedstock molecules absorb most at short (∼200 nm) wavelengths, with decreasing UV absorption at longer wavelengths. For comparison, we also measured the nucleobase adenine and found that adenine absorbs significantly more than the simpler molecules often invoked in prebiotic synthesis. Our results enable the calculation of UV photon penetration under varying chemical scenarios and allow further constraints on plausibility and self-consistency of such scenarios. While the precise path that prebiotic chemistry took remains elusive, improved understanding of the UV environment in prebiotically plausible waters can help constrain both the chemistry and the environmental conditions that may allow such chemistry to occur.

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 venusian atmosphere and then describe the atmospheric chemical anomalies and how they motivate future astrobiology missions to Venus.

Assessment of Ammonia as a Biosignature Gas in Exoplanet Atmospheres.

Ammonia (NH3) in a terrestrial planet atmosphere is generally a good biosignature gas, primarily because terrestrial planets have no significant known abiotic NH3 source. The conditions required for NH3 to accumulate in the atmosphere are, however, stringent. NH3's high water solubility and high biousability likely prevent NH3 from accumulating in the atmosphere to detectable levels unless life is a net source of NH3 and produces enough NH3 to saturate the surface sinks. Only then can NH3 accumulate in the atmosphere with a reasonable surface production flux. For the highly favorable planetary scenario of terrestrial planets with hydrogen (H2)-dominated atmospheres orbiting M dwarf stars (M5V), we find that a minimum of about 5 ppm column-averaged mixing ratio is needed for NH3 to be detectable with JWST, considering a 10 ppm JWST systematic noise floor. When the surface is saturated with NH3 (i.e., there are no NH3-removal reactions on the surface), the required biological surface flux to reach 5 ppm is on the order of 1010 molecules/(cm2·s), comparable with the terrestrial biological production of methane (CH4). However, when the surface is unsaturated with NH3, due to additional sinks present on the surface, life would have to produce NH3 at surface flux levels on the order of 1015 molecules/(cm2·s) (∼4.5 × 106 Tg/year). This value is roughly 20,000 times greater than the biological production of NH3 on the Earth and about 10,000 times greater than Earth's CH4 biological production. Volatile amines have similar solubilities and reactivities to NH3 and hence share NH3's weaknesses and strengths as a biosignature. Finally, to establish NH3 as a biosignature gas, we must rule out mini-Neptunes with deep atmospheres, where temperatures and pressures are high enough for NH3's atmospheric production.

UV Transmission in Natural Waters on Prebiotic Earth.

Ultraviolet (UV) light plays a key role in surficial theories of the origin of life, and numerous studies have focused on constraining the atmospheric transmission of UV radiation on early Earth. However, the UV transmission of the natural waters in which origins-of-life chemistry (prebiotic chemistry) is postulated to have occurred is poorly constrained. In this work, we combine laboratory and literature-derived absorption spectra of potential aqueous-phase prebiotic UV absorbers with literature estimates of their concentrations on early Earth to constrain the prebiotic UV environment in marine and terrestrial natural waters, and we consider the implications for prebiotic chemistry. We find that prebiotic freshwaters were largely transparent in the UV, contrary to assumptions in some models of prebiotic chemistry. Some waters, such as high-salinity waters like carbonate lakes, may be deficient in shortwave (≤220 nm) UV flux. More dramatically, ferrous waters can be strongly UV-shielded, particularly if the Fe2+ forms highly UV-absorbent species such as FeCN64-. Such waters may be compelling venues for UV-averse origin-of-life scenarios but are unfavorable for some UV-dependent prebiotic chemistries. UV light can trigger photochemistry even if attenuated through photochemical transformations of the absorber (e.g., eaq- production from halide irradiation), which may have both constructive and destructive effects for prebiotic syntheses. Prebiotic chemistries that invoke waters that contain such absorbers must self-consistently account for the chemical effects of these transformations. The speciation and abundance of Fe2+ in natural waters on early Earth is a major uncertainty and should be prioritized for further investigation, as it played a major role in UV transmission in prebiotic natural waters.

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 modeled 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 nonequilibrium processes. None of these potential phosphine production pathways is 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.

Assessment of Isoprene as a Possible Biosignature Gas in Exoplanets with Anoxic Atmospheres.

The search for possible biosignature gases in habitable exoplanet atmospheres is accelerating, although actual observations are likely years away. This work adds isoprene, C5H8, to the roster of biosignature gases. We found that isoprene geochemical formation is highly thermodynamically disfavored and has no known abiotic false positives. The isoprene production rate on Earth rivals that of methane (CH4; ∼500 Tg/year). Unlike methane, on Earth isoprene is rapidly destroyed by oxygen-containing radicals. Although isoprene is predominantly produced by deciduous trees, isoprene production is ubiquitous to a diverse array of evolutionary distant organisms, from bacteria to plants and animals-few, if any, volatile secondary metabolites have a larger evolutionary reach. Although non-photochemical sinks of isoprene may exist, such as degradation of isoprene by life or other high deposition rates, 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 ultraviolet fluxes. Limited by an assumed 10 ppm instrument noise floor, habitable atmosphere characterization when using James Webb Space Telescope (JWST) is only achievable with a 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 the 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 isoprene spectral features are hard to distinguish from those of methane and also from other hydrocarbons containing the isoprene substructure. Despite these challenges, isoprene is worth adding to the menu of potential biosignature gases.

The role of the three body photodissociation channel of water in the evolution of dioxygen in astrophysical applications.

A recent experiment at the Dalian Coherent Light Source (DCLS) has provided measurements of the partial cross sections for the photodissociation of water vapor over an unprecedented range of wavelengths in the vacuum ultraviolet (VUV) region. It was found that the three body dissociation channel, H + H + O(3P/1D), becomes prominent at wavelengths shorter than the Lyman α-line at 121.6 nm. The present work explores the kinetic consequences of this discovery for several astrophysically motivated examples. The irradiation of a dilute low-temperature gas by unscreened solar radiation, similar to early stage photochemical processing in a comet coma, shows significant increase in the production of O2-molecules at shorter times, <1 day, that might physically correspond to the photochemical reaction zone of the coma. Several examples of planetary atmospheres show increased O-atom production at high altitudes but relatively little modification of the equilibrium O2 concentrations predicted by conventional models.

The Venusian Lower Atmosphere Haze as a Depot for Desiccated Microbial Life: A Proposed Life Cycle for Persistence of the Venusian Aerial Biosphere.

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 venusian 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 venusian 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.

Ultraviolet-Driven Deamination of Cytidine Ribonucleotides Under Planetary Conditions.

A previously proposed synthesis of pyrimidine ribonucleotides makes use of ultraviolet (UV) light to convert ß-d-ribocytidine-2',3'-cyclic phosphate to ß-d-ribouridine-2',3'-cyclic phosphate, while simultaneously selectively degrading synthetic byproducts. Past studies of the photochemical reactions of pyrimidines have employed mercury arc lamps, characterized by narrowband emission centered at 254 nm, which is not representative of the UV environment of the early Earth. To further assess this process under more realistic circumstances, we investigated the wavelength dependence of the UV-driven conversion of ß-d-ribocytidine-2',3'-cyclic phosphate to ß-d-ribouridine-2',3'-cyclic phosphate. We used constraints provided by planetary environments to assess the implications for pyrimidine nucleotides on the early Earth. We found that the wavelengths of light (255-285 nm) that most efficiently drive the deamination of ß-d-ribocytidine-2',3'-cyclic phosphate to ß-d-ribouridine-2',3'-cyclic phosphate are accessible on planetary surfaces such as those of the Hadean-Archaean Earth for CO2-N2-dominated atmospheres. However, continued irradiation could eventually lead to low levels of ribocytidine in a low-temperature, highly irradiated environment, if production rates are slow.

Phosphine as a Biosignature Gas in Exoplanet Atmospheres.

A long-term goal of exoplanet studies is the identification and detection of biosignature gases. Beyond the most discussed biosignature gas O2, only a handful of gases have been considered in detail. In this study, we evaluate phosphine (PH3). On Earth, PH3 is associated with anaerobic ecosystems, and as such, it is a potential biosignature gas in anoxic exoplanets. We simulate the atmospheres of habitable terrestrial planets with CO2- and H2-dominated atmospheres and find that PH3 can accumulate to detectable concentrations on planets with surface production fluxes of 1010 to 1014 cm-2 s-1 (corresponding to surface concentrations of 10s of ppb to 100s of ppm), depending on atmospheric composition and ultraviolet (UV) irradiation. While high, the surface flux values are comparable to the global terrestrial production rate of methane or CH4 (1011 cm-2 s-1) and below the maximum local terrestrial PH3 production rate (1014 cm-2 s-1). As with other gases, PH3 can more readily accumulate on low-UV planets, for example, planets orbiting quiet M dwarfs or with a photochemically generated UV shield. PH3 has three strong spectral features such that in any atmosphere scenario one of the three will be unique compared with other dominant spectroscopic molecules. Phosphine's weakness as a biosignature gas is its high reactivity, requiring high outgassing rates for detectability. We calculate that tens of hours of JWST (James Webb Space Telescope) time are required for a potential detection of PH3. Yet, because PH3 is spectrally active in the same wavelength regions as other atmospherically important molecules (such as H2O and CH4), searches for PH3 can be carried out at no additional observational cost to searches for other molecular species relevant to characterizing exoplanet habitability. Phosphine is a promising biosignature gas, as it has no known abiotic false positives on terrestrial planets from any source that could generate the high fluxes required for detection.

Photochemical reductive homologation of hydrogen cyanide using sulfite and ferrocyanide.

Photoredox cycling during UV irradiation of ferrocyanide ([FeII(CN)6]4-) in the presence of stoichiometric sulfite (SO32-) is shown to be an extremely effective way to drive the reductive homologation of hydrogen cyanide (HCN) to simple sugars and precursors of hydroxy acids and amino acids.

Sulfidic Anion Concentrations on Early Earth for Surficial Origins-of-Life Chemistry.

A key challenge in origin-of-life studies is understanding the environmental conditions on early Earth under which abiogenesis occurred. While some constraints do exist (e.g., zircon evidence for surface liquid water), relatively few constraints exist on the abundances of trace chemical species, which are relevant to assessing the plausibility and guiding the development of postulated prebiotic chemical pathways which depend on these species. In this work, we combine literature photochemistry models with simple equilibrium chemistry calculations to place constraints on the plausible range of concentrations of sulfidic anions (HS-, HSO3-, SO32-) available in surficial aquatic reservoirs on early Earth due to outgassing of SO2 and H2S and their dissolution into small shallow surface water reservoirs like lakes. We find that this mechanism could have supplied prebiotically relevant levels of SO2-derived anions, but not H2S-derived anions. Radiative transfer modeling suggests UV light would have remained abundant on the planet surface for all but the largest volcanic explosions. We apply our results to the case study of the proposed prebiotic reaction network of Patel et al. ( 2015 ) and discuss the implications for improving its prebiotic plausibility. In general, epochs of moderately high volcanism could have been especially conducive to cyanosulfidic prebiotic chemistry. Our work can be similarly applied to assess and improve the prebiotic plausibility of other postulated surficial prebiotic chemistries that are sensitive to sulfidic anions, and our methods adapted to study other atmospherically derived trace species.

Solvated-electron production using cyanocuprates is compatible with the UV-environment on a Hadean-Archaean Earth.

UV-driven photoredox processing of cyanocuprates can generate simple sugars necessary for prebiotic synthesis. We investigate the wavelength dependence of this process from 215 to 295 nm and generally observe faster rates at shorter wavelengths. The most efficient wavelengths are accessible to a range of potential prebiotic atmospheres, supporting the potential role of cyanocuprate photochemistry in prebiotic synthesis on the early Earth.

Atmospheric Constraints on the Surface UV Environment of Mars at 3.9 Ga Relevant to Prebiotic Chemistry.

Recent findings suggest that Mars may have been a clement environment for the emergence of life and may even have compared favorably to Earth in this regard. These findings have revived interest in the hypothesis that prebiotically important molecules or even nascent life may have formed on Mars and been transferred to Earth. UV light plays a key role in prebiotic chemistry. Characterizing the early martian surface UV environment is key to understanding how Mars compares to Earth as a venue for prebiotic chemistry. Here, we present two-stream, multilayer calculations of the UV surface radiance on Mars at 3.9 Ga to constrain the surface UV environment as a function of atmospheric state. We explore a wide range of atmospheric pressures, temperatures, and compositions that correspond to the diversity of martian atmospheric states consistent with available constraints. We include the effects of clouds and dust. We calculate dose rates to quantify the effect of different atmospheric states on UV-sensitive prebiotic chemistry. We find that, for normative clear-sky CO2-H2O atmospheres, the UV environment on young Mars is comparable to young Earth. This similarity is robust to moderate cloud cover; thick clouds (τcloud ≥ 100) are required to significantly affect the martian UV environment, because cloud absorption is degenerate with atmospheric CO2. On the other hand, absorption from SO2, H2S, and dust is nondegenerate with CO2, meaning that, if these constituents build up to significant levels, surface UV fluence can be suppressed. These absorbers have spectrally variable absorption, meaning that their presence affects prebiotic pathways in different ways. In particular, high SO2 environments may admit UV fluence that favors pathways conducive to abiogenesis over pathways unfavorable to it. However, better measurements of the spectral quantum yields of these pathways are required to evaluate this hypothesis definitively. Key Words: Radiative transfer-Origin of life-Mars-UV radiation-Prebiotic chemistry. Astrobiology 17, 687-708.

Constraints on the Early Terrestrial Surface UV Environment Relevant to Prebiotic Chemistry.

The UV environment is a key boundary condition to abiogenesis. However, considerable uncertainty exists as to planetary conditions and hence surface UV at abiogenesis. Here, we present two-stream multilayer clear-sky calculations of the UV surface radiance on Earth at 3.9 Ga to constrain the UV surface fluence as a function of albedo, solar zenith angle (SZA), and atmospheric composition. Variation in albedo and latitude (through SZA) can affect maximum photoreaction rates by a factor of >10.4; for the same atmosphere, photoreactions can proceed an order of magnitude faster at the equator of a snowball Earth than at the poles of a warmer world. Hence, surface conditions are important considerations when computing prebiotic UV fluences. For climatically reasonable levels of CO2, fluence shortward of 189 nm is screened out, meaning that prebiotic chemistry is robustly shielded from variations in UV fluence due to solar flares or variability. Strong shielding from CO2 also means that the UV surface fluence is insensitive to plausible levels of CH4, O2, and O3. At scattering wavelengths, UV fluence drops off comparatively slowly with increasing CO2 levels. However, if SO2 and/or H2S can build up to the ≥1-100 ppm level as hypothesized by some workers, then they can dramatically suppress surface fluence and hence prebiotic photoprocesses. H2O is a robust UV shield for λ < 198 nm. This means that regardless of the levels of other atmospheric gases, fluence ≲198 nm is only available for cold, dry atmospheres, meaning sources with emission ≲198 (e.g., ArF excimer lasers) can only be used in simulations of cold environments with low abundance of volcanogenic gases. On the other hand, fluence at 254 nm is unshielded by H2O and is available across a broad range of [Formula: see text], meaning that mercury lamps are suitable for initial studies regardless of the uncertainty in primordial H2O and CO2 levels. Key Words: Radiative transfer-Origin of life-Planetary environments-UV radiation-Prebiotic chemistry. Astrobiology 17, 169-204.

Influence of the UV Environment on the Synthesis of Prebiotic Molecules.

Ultraviolet radiation is common to most planetary environments and could play a key role in the chemistry of molecules relevant to abiogenesis (prebiotic chemistry). In this work, we explore the impact of UV light on prebiotic chemistry that might occur in liquid water on the surface of a planet with an atmosphere. We consider effects including atmospheric absorption, attenuation by water, and stellar variability to constrain the UV input as a function of wavelength. We conclude that the UV environment would be characterized by broadband input, and wavelengths below 204 nm and 168 nm would be shielded out by atmospheric CO2 and water, respectively. We compare this broadband prebiotic UV input to the narrowband UV sources (e.g., mercury lamps) often used in laboratory studies of prebiotic chemistry and explore the implications for the conclusions drawn from these experiments. We consider as case studies the ribonucleotide synthesis pathway of Powner et al. (2009) and the sugar synthesis pathway of Ritson and Sutherland (2012). Irradiation by narrowband UV light from a mercury lamp formed an integral component of these studies; we quantitatively explore the impact of more realistic UV input on the conclusions that can be drawn from these experiments. Finally, we explore the constraints solar UV input places on the buildup of prebiotically important feedstock gasses like CH4 and HCN. Our results demonstrate the importance of characterizing the wavelength dependence (action spectra) of prebiotic synthesis pathways to determine how pathways derived under laboratory irradiation conditions will function under planetary prebiotic conditions.