A key challenge in origins‐of‐life studies is estimating the abundances of species relevant to the chemical pathways proposed to have contributed to the emergence of life on early Earth. Dissolved nitrogen oxide anions ( ), in particular nitrate ( ) and nitrite ( ), have been invoked in diverse origins‐of‐life chemistry, from the oligomerization of RNA to the emergence of protometabolism. Recent work has calculated the supply of from the prebiotic atmosphere to the ocean and reported steady state [ ] to be high across all plausible parameter space. These findings rest on the assumption that is stable in natural waters unless processed at a hydrothermal vent. Here, we show that is unstable in the reducing environment of early Earth. Sinks due to ultraviolet photolysis and reactions with reduced iron (Fe2+) suppress [ ] by several orders of magnitude relative to past predictions. For pH = 6.5–8 and T = 0–50 °C, we find that it is most probable that [ ] <1μM in the prebiotic ocean. On the other hand, prebiotic ponds with favorable drainage characteristics may have sustained [ ] ≥1μM. As on modern Earth, most on prebiotic Earth should have been present as , due to its much greater stability. These findings inform the kind of prebiotic chemistries that would have been possible on early Earth. We discuss the implications for proposed prebiotic chemistries and highlight the need for further studies of kinetics to reduce the considerable uncertainties in predicting [ ] on early 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.
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.
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.
Potentially habitable planets orbiting M dwarfs are of intense astrobiological interest because they are the only rocky worlds accessible to biosignature search over the next 10+ years because of a confluence of observational effects. Simultaneously, recent experimental and theoretical work suggests that UV light may have played a key role in the origin of life on Earth, especially the origin of RNA. Characterizing the UV environment on M-dwarf planets is important for understanding whether life as we know it could emerge on such worlds. In this work, we couple radiative transfer models to observed M-dwarf spectra to determine the UV environment on prebiotic Earth-analog planets orbiting M dwarfs. We calculate dose rates to quantify the impact of different host stars on prebiotically important photoprocesses. We find that M-dwarf planets have access to 100–1000 times less bioactive UV fluence than the young Earth. It is unclear whether UV-sensitive prebiotic chemistry that may have been important to abiogenesis, such as the only known prebiotically plausible pathways for pyrimidine ribonucleotide synthesis, could function on M-dwarf planets. This uncertainty affects objects like the recently discovered habitable-zone planets orbiting Proxima Centauri, TRAPPIST-1, and LHS 1140. Laboratory studies of the sensitivity of putative prebiotic pathways to irradiation level are required to resolve this uncertainty. If steadystate M-dwarf UV output is insufficient to power these pathways, transient elevated UV irradiation due to flares may suffice; laboratory studies can constrain this possibility as well.
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.
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 , meaning that mercury lamps are suitable for initial studies regardless of the uncertainty in primordial H2O and CO2 levels.
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.
We have used Hubble/WFC3 and the G141 grism to measure the secondary eclipse of the transiting, very hot Jupiter CoRoT-2b in the 1.1-1.7 μm spectral region. We find an eclipse depth averaged over this band equal to parts per million, equivalent to a blackbody temperature of 1788 ± 18 K. We study and characterize several WFC3 instrumental effects, especially the "hook" phenomenon described by Deming et al. We use data from several transiting exoplanet systems to find a quantitative relation between the amplitude of the hook and the exposure level of a given pixel. Although the uncertainties in this relation are too large to allow us to develop an empirical correction for our data, our study provides a useful guide for optimizing exposure levels in future WFC3 observations. We derive the planet's spectrum using a differential method. The planet-to-star contrast increases to longer wavelength within the WFC3 bandpass, but without water absorption or emission to a 3σ limit of 85 ppm. The slope of the WFC3 spectrum is significantly less than the slope of the best-fit blackbody. We compare all existing eclipse data for this planet to a blackbody spectrum, and to spectra from both solar abundance and carbon-rich (C/O = 1) models. A blackbody spectrum is an acceptable fit to the full data set. Extra continuous opacity due to clouds or haze, and flattened temperature profiles, are strong candidates to produce quasi-blackbody spectra, and to account for the amplitude of the optical eclipses. Our results show ambiguous evidence for a temperature inversion in this planet.
We probe the structure and composition of the atmospheres of five hot Jupiter exoplanets using the Hubble Space Telescope Wide Field Camera 3 (WFC3) instrument. We use the G141 grism (1.1-1.7 μm) to study TrES-2b, TrES-4b, and CoRoT-1b in transit; TrES-3b in secondary eclipse; and WASP-4b in both. This wavelength region includes a predicted absorption feature from water at 1.4 μm, which we expect to be nondegenerate with the other molecules that are likely to be abundant for hydrocarbon-poor (e.g., solar composition) hot Jupiter atmospheres. We divide our wavelength regions into 10 bins. For each bin we produce a spectrophotometric light curve spanning the time of transit or eclipse. We correct these light curves for instrumental systematics without reference to an instrument model. For our transmission spectra, our mean 1σ precision per bin corresponds to variations of 2.1, 2.8, and 3.0 atmospheric scale heights for TrES-2b, TrES-4b, and CoRoT-1b, respectively. We find featureless spectra for these three planets. We are unable to extract a robust transmission spectrum for WASP-4b. For our dayside emission spectra, our mean 1σ precision per bin corresponds to a planet-to-star flux ratio of 1.5 × 10–4 and 2.1 × 10–4 for WASP-4b and TrES-3b, respectively. We combine these estimates with previous broadband measurements and conclude that for both planets isothermal atmospheres are disfavored. We find no signs of features due to water. We confirm that WFC3 is suitable for studies of transiting exoplanets, but in staring mode multivisit campaigns are necessary to place strong constraints on water abundance.
Exoplanetary transmission spectroscopy in the near-infrared using the Hubble Space Telescope(HST) NICMOS is currently ambiguous because different observational groups claim different results from the same data, depending on their analysis methodologies. Spatial scanning with HST/WFC3 provides an opportunity to resolve this ambiguity. We here report WFC3 spectroscopy of the giant planets HD 209458b and XO-1b in transit, using spatial scanning mode for maximum photon-collecting efficiency. We introduce an analysis technique that derives the exoplanetary transmission spectrum without the necessity of explicitly decorrelating instrumental effects, and achieves nearly photon-limited precision even at the high flux levels collected in spatial scan mode. Our errors are within 6% (XO-1) and 26% (HD 209458b) of the photon-limit at a resolving power of λ/δλ ~ 70, and are better than 0.01% per spectral channel. Both planets exhibit water absorption of approximately 200 ppm at the water peak near 1.38 μm. Our result for XO-1b contradicts the much larger absorption derived from NICMOS spectroscopy. The weak water absorption we measure for HD 209458b is reminiscent of the weakness of sodium absorption in the first transmission spectroscopy of an exoplanet atmosphere by Charbonneau et al. Model atmospheres having uniformly distributed extra opacity of 0.012 cm2 g–1 account approximately for both our water measurement and the sodium absorption. Our results for HD 209458b support the picture advocated by Pont et al. in which weak molecular absorptions are superposed on a transmission spectrum that is dominated by continuous opacity due to haze and/or dust. However, the extra opacity needed for HD 209458b is grayer than for HD 189733b, with a weaker Rayleigh component.
Many pulsating phenomena are associated with the auroral substorm. It has been considered that some of these phenomena involve kilometer-scale Alfvén waves coupling the magnetosphere and ionosphere. Electric field oscillations at the altitude of the ionosphere are a signature of such wave activity that could distinguish it from other sources of auroral particle precipitation, which may be simply tracers of magnetospheric activity. Therefore, a ground based diagnostic of kilometer-scale oscillating electric fields would be a valuable tool in the study of pulsations and the auroral substorm. In this study we attempt to develop such a tool in the Poker Flat incoherent scatter radar (PFISR). The central result is a statistically significant detection of a 1.4 Hz electric field oscillation associated with a similar oscillating optical emission, during the recovery phase of a substorm. The optical emissions also contain a bright, lower frequency (0.2 Hz) pulsation that does not show up in the radar backscatter. The fact that higher frequency oscillations are detected by the radar, whereas the bright, lower frequency optical pulsation is not detected by the radar, serves to strengthen a theoretical argument that the radar is sensitive to oscillating electric fields, but not to oscillating particle precipitation. Although it is difficult to make conclusions as to the physical mechanism, we do not find evidence for a plane-wave-like Alfvén wave; the detected structure is evident in only two of five adjacent beams. We emphasize that this is a new application for ISR, and that corroborating results are needed.
Polar Mesosphere Summer Echoes (PMSE) occur near the mesopause during the polar summer months. PMSE are primarily studied at VHF, however there have been some detections at higher frequencies. Here, we report on some of the first detections of PMSE with the 450 MHz (67 cm) Poker Flat Advanced Modular Incoherent Scatter Radar (PFISR). Echoes were observed with volume reflectivities (radar scattering cross section per unit volume) near 2–3 × 10−17 m−1. On 11 June 2007, PFISR was operating in a 26‐beam position mode, with look directions spread over an approximately 80 by 80 km2 region at 85 km altitude with elevation angles as low as ∼50°. The measurements showed patchy (tens of kilometer) irregularity regions drifting in from the north, in addition to smaller, more localized structures. There was no evidence for strong aspect sensitivity of these UHF echoes, as PMSE was observed in all look directions with relatively uniform intensity. The observations indicate the presence of fossilized irregularities drifting with the background wind field as well as areas of developing irregularities possibly associated with the presence of active neutral air turbulence.