arXiv subjects

Paul B. Rimmer

Publications and source records attributed to Paul B. Rimmer.

At least 37 records · Page 2Linked to original sources

arXiv2023

Origins of Life on Exoplanets

I show that exoplanets can be used to test origins scenarios. Origins scenarios start with certain initial conditions, proceed via a network of chemical reactions and, if successful, result in a chemistry that is closer to a living system than the initial conditions. Exoplanet environments can be applied to test each of these three aspects of origins scenarios. I show what tests can be applied to the UV-driven cyanosulfidic scenario and how the application of some of these tests has already falsified certain versions of this scenario. Testing initial conditions has replaced certain reactants with others and has affected the overall chemical network underlying the cyanosulfidic scenario. The sequence of reactions the scenario invokes provide a predicted upper limit on the ubiquity of life in the universe that has ample room for improvement. The outcome of the experiments in different environments is part of a predicted distribution of biosignature detections that can be compared to future observed distributions.

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arXiv2023

Growth and Evolution of Secondary Volcanic Atmospheres: II. The Importance of Kinetics

Volcanism is a major and long-term source of volatile elements such as C and H to Earth's atmosphere, likely has been to Venus's atmosphere, and may be for exoplanets. Models simulating volcanic growth of atmospheres often make one of two assumptions: either that atmospheric speciation is set by the high-temperature equilibrium of volcanism; or, that volcanic gases thermochemically re-equilibrate to the new, lower, temperature of the surface environment. In the latter case it has been suggested that volcanic atmospheres may create biosignature false positives. Here, we test the assumptions underlying such inferences by performing chemical kinetic calculations to estimate the relaxation timescale of volcanically-derived atmospheres to thermochemical equilibrium, in a simple 0D atmosphere neglecting photochemistry and reaction catalysis. We demonstrate that for planets with volcanic atmospheres, thermochemical equilibrium over geological timescales can only be assumed if the atmospheric temperature is above ~700K. Slow chemical kinetics at lower temperatures inhibit the relaxation of redox-sensitive species to low-temperature thermochemical equilibrium, precluding the production of two independent biosignatures through thermochemistry alone: 1. ammonia, and 2. the co-occurrence of CO$_2$ and CH$_4$ in an atmosphere in the absence of CO. This supports the use of both biosignatures for detecting life. Quenched at the high temperature of their degassing, volcanic gases also have speciations characteristic of those produced from a more oxidized mantle, if interpreted as being at thermochemical equilibrium. This therefore complicates linking atmospheres to the interiors of rocky exoplanets, even when their atmospheres are purely volcanic in origin.

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arXiv2022

Ammonia and Phosphine in the Clouds of Venus as Potentially Biological Anomalies

We are of the opinion that several anomalies in the atmosphere of Venus provide evidence of yet-unknown processes and systems that are out of equilibrium. The investigation of these anomalies on Venus should be open to the wide range of explanations, including unknown biological activity. We provide an overview of two anomalies, the tentative detection of ammonia and phosphine in Venus's atmosphere. These anomalies fly in the face of the tacit assumption that the atmosphere of Venus must be in chemical redox equilibrium, an assumption connected to the belief that Venus is lifeless. We then discuss several major past discoveries in astronomy, biology and geology, which lead to the abandonment of certain assumptions held by many scientists as though they were well-established principles. The anomalies of ammonia and phosphine in the atmosphere of Venus are placed in the context of these historical discoveries. This context supports our opinion that persistence by the community in the exploration of these anomalies with a skeptical eye towards tacit assumptions will increase the chances of making profound discoveries about the atmosphere of Venus and the diverse and often strange nature of planetary environments.

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arXiv2022

Growth and evolution of secondary volcanic atmospheres: I. Identifying the geological character of hot rocky planets

The geology of Earth and super-Earth sized planets will, in many cases, only be observable via their atmospheres. Here, we investigate secondary volcanic atmospheres as a key base case of how atmospheres may reflect planetary geochemistry. We couple volcanic outgassing with atmospheric chemistry models to simulate the growth of C-O-H-S-N atmospheres in thermochemical equilibrium, focusing on what information about a planet's mantle fO$_2$ and bulk silicate H/C ratio could be determined by atmospheric observation. 800K volcanic atmospheres develop distinct compositional groups as the mantle fO$_2$ is varied, which can be identified using sets of (often minor) indicator species: Class O, representing an oxidised mantle and containing SO$_2$ and sulfur allotropes; Class I, formed by intermediate mantle fO$_2$'s and containing CO$_2$, CH$_4$, CO and COS; and Class R, produced by reduced mantles, containing H$_2$, NH$_3$ and CH$_4$. These atmospheric classes are robust to a wide range of bulk silicate H/C ratios. However, the H/C ratio does affect the dominant atmospheric constituent, which can vary between H$_2$, H$_2$O and CO$_2$ once the chemical composition has stabilised to a point where it no longer changes substantially with time. This final atmospheric state is dependent on the mantle fO$_2$, the H/C ratio, and time since the onset of volcanism. The atmospheric classes we present are appropriate for the closed-system growth of hot exoplanets, and may be used as a simple base for future research exploring the effects of other open-system processes on secondary volcanic atmospheres.

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arXiv2022

Low levels of sulphur dioxide contamination of Venusian phosphine spectra

New analysis is presented of the 1.1 mm wavelength absorption lines in Venus' atmosphere that suggested the presence of phosphine. We retrieve a sulphur dioxide observation from the JCMT archive that was simultaneous within a few days of the PH3 1-0 spectrum obtained in June 2017, and demonstrate via a radiative transfer calculation that contamination of PH3 by SO2 was ~10 per cent. We also present ALMA 2019 spectra of PH3 1-0 and an SO2 transition acquired simultaneously, and infer that SO2 line-contamination was ~2 percent (for the least-noisy half of the planetary disc). The contamination-subtracted ALMA and JCMT spectra (of 6-8 sigma confidence) are now consistent with similar absorption-depths at the two epochs. The two values span -1.9(+/-0.2) 10-4 of the continuum signal (which was re-estimated for ALMA), albeit for differing planetary areas. This suggests that the abundance attributed to phosphine in Venus' atmosphere was broadly similar in 2017 and 2019.

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arXiv2022

Proposed energy-metabolisms cannot explain the atmospheric chemistry of Venus

Life in the clouds of Venus, if present in sufficiently high abundance, must be affecting the atmospheric chemistry. It has been proposed that abundant Venusian life could obtain energy from its environment using three possible sulfur energy-metabolisms. These metabolisms raise the possibility of Venus's enigmatic cloud-layer SO$_2$-depletion being caused by life. We here couple each proposed energy-metabolism to a photochemical-kinetics code and self-consistently predict the composition of Venus's atmosphere under the scenario that life produces the observed SO$_2$-depletion. Using this photo-bio-chemical kinetics code, we show that all three metabolisms can produce SO$_2$-depletions, but do so by violating other observational constraints on Venus's atmospheric chemistry. We calculate the maximum possible biomass density of sulfur-metabolising life in the clouds, before violating observational constraints, to be $\sim10^{-5}\,-\,10^{-3}\,{\rm mg\,m^{-3}}$. The methods employed are equally applicable to aerial biospheres on Venus-like exoplanets, planets that are optimally poised for atmospheric characterisation in the near future.

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arXiv2022

Constraints on the production of phosphine by Venusian volcanoes

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

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arXiv2021

Production of Ammonia Makes Venusian Clouds Habitable and Explains Observed Cloud-Level Chemical Anomalies

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 new 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 semi-solid ammonium salt slurries, with a pH~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.

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arXiv2021

Venusian phosphine: a 'Wow!' signal in chemistry?

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.

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arXiv2021

Detectable Abundance of Cyanoacetylene (HC$_3$N) Predicted on Reduced Nitrogen-Rich Super-Earth Atmospheres

We predict that cyanoacetylene (HC$_3$N) is produced photochemically in the atmosphere of GJ 1132 b in abundances detectable by the James Webb Space Telescope (JWST), assuming that the atmosphere is hydrogen dominated and rich in molecular nitrogen (N$_2$), methane (CH$_4$) and hydrogen cyanide (HCN), as described by Swain et al. (2021). First, we construct line list and cross-sections for HC$_3$N. Then we apply these cross-sections and the model atmosphere of Swain et al. (2021) to a radiative transfer model in order to simulate the transmission spectrum of GJ 1132 b as it would be seen by JWST, accounting for the uncertainty in the retrieved abundances. We predict that cyanoacetylene features at various wavelengths, with a clear lone feature at 4.5 $μ$m, observable by JWST after one transit. This feature persists within the $1-σ$ uncertainty of the retrieved abundances of HCN and CH$_4$. The signal is detectable for stratospheric temperatures $\lesssim 600$ K and moderate stratospheric mixing ($10^6 \, {\rm cm^2 \, s^{-1}} \lesssim K_{zz} \lesssim 10^8 \, {\rm cm^2 \, s^{-1}}$). Our results also indicate that HC$_3$N is an important source of opacity that future retrieval models should consider.

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arXiv2021

Photochemistry of Venus-Like Planets Orbiting K- and M-Dwarf Stars

Compared to the diversity seen in exoplanets, Venus is a veritable astrophysical twin of the Earth, however its global cloud layer truncates features in transmission spectroscopy, masking its non-Earth-like nature. Observational indicators that can distinguish an exo-Venus from an exo-Earth must therefore survive above the cloud layer. The above-cloud atmosphere is dominated by photochemistry, which depends on the spectrum of the host star and therefore changes between stellar systems. We explore the systematic changes in photochemistry above the clouds of Venus-like exoplanets orbiting K-Dwarf or M-Dwarf host stars, using a recently validated model of the full Venus atmosphere (0-115 km) and stellar spectra from the MUSCLES Treasury survey. SO2, OCS and H2S are key gas species in Venus-like planets that are not present in Earth-like planets, and could therefore act as observational discriminants if their atmospheric abundances are high enough to be detected. We find that SO2, OCS and H2S all survive above the cloud layer when irradiated by the coolest K-Dwarf and all seven M-Dwarfs, whereas these species are heavily photochemically depleted above the clouds of Venus. The production of sulfuric acid molecules that form the cloud layer decreases for decreasing stellar effective temperature. Less steady-state photochemical oxygen and ozone forms with decreasing stellar effective temperature, and the effect of chlorine-catalysed reaction cycles diminish in favour of HOx and SOx catalysed cycles. We conclude that trace sulfur gases will be prime observational indicators of Venus-like exoplanets around M-Dwarf host stars, potentially capable of distinguishing an exo-Venus from an exo-Earth.

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arXiv2021

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 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.

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arXiv2021

MOVES IV. Modelling the influence of stellar XUV-flux, cosmic rays, and stellar energetic particles on the atmospheric composition of the hot Jupiter HD 189733b

Hot Jupiters provide valuable natural laboratories for studying potential contributions of high-energy radiation to prebiotic synthesis in the atmospheres of exoplanets. In this fourth paper of the MOVES (Multiwavelength Observations of an eVaporating Exoplanet and its Star) programme, we study the effect of different types of high-energy radiation on the production of organic and prebiotic molecules in the atmosphere of the hot Jupiter HD 189733b. Our model combines X-ray and UV observations from the MOVES programme and 3D climate simulations from the 3D Met Office Unified Model to simulate the atmospheric composition and kinetic chemistry with the STAND2019 network. Also, the effects of galactic cosmic rays and stellar energetic particles are included. We find that the differences in the radiation field between the irradiated dayside and the shadowed nightside lead to stronger changes in the chemical abundances than the variability of the host star's XUV emission. We identify ammonium (NH4+) and oxonium (H3O+) as fingerprint ions for the ionization of the atmosphere by both galactic cosmic rays and stellar particles. All considered types of high-energy radiation have an enhancing effect on the abundance of key organic molecules such as hydrogen cyanide (HCN), formaldehyde (CH2O), and ethylene (C2H4). The latter two are intermediates in the production pathway of the amino acid glycine (C2H5NO2) and abundant enough to be potentially detectable by JWST.

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arXiv2021

Hydroxide salts in the clouds of Venus: their effect on the sulfur cycle and cloud droplet pH

The depletion of SO$_2$ and H$_2$O in and above the clouds of Venus (45 -- 65 km) cannot be explained by known gas-phase chemistry and the observed composition of the atmosphere. We apply a full-atmosphere model of Venus to investigate three potential explanations for the SO$_2$ and H$_2$O depletion: (1) varying the below-cloud water vapor (H$_2$O), (2) varying the below-cloud sulfur dioxide (SO$_2$), and (3) the incorporation of chemical reactions inside the sulfuric acid cloud droplets. We find that increasing the below-cloud H$_2$O to explain the SO$_2$ depletion results in a cloud top that is 20 km too high, above-cloud O$_2$ three orders of magnitude greater than observational upper limits and no SO above 80 km. The SO$_2$ depletion can be explained by decreasing the below-cloud SO$_2$ to $20\,{\rm ppm}$. The depletion of SO$_2$ in the clouds can also be explained by the SO$_2$ dissolving into the clouds, if the droplets contain hydroxide salts. These salts buffer the cloud pH. The amount of salts sufficient to explain the SO$_2$ depletion entail a droplet pH of $\sim 1$ at 50 km. Since sulfuric acid is constantly condensing out into the cloud droplets, there must be a continuous and pervasive flux of salts of $\approx 10^{-13} \, {\rm mol \, cm^{-2} \, s^{-1}}$ driving the cloud droplet chemistry. An atmospheric probe can test both of these explanations by measuring the pH of the cloud droplets and the concentrations of gas-phase SO$_2$ below the clouds.

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arXiv2020

On the Robustness of Phosphine Signatures in Venus' Clouds

We published spectra of phosphine molecules in Venus' clouds, following open-science principles in releasing data and scripts (with community input leading to ALMA re-processing, now benefiting multiple projects). Some misconceptions about de-trending of spectral baselines have also emerged, which we address here. Using the JCMT PH3-discovery data, we show that mathematically-correct polynomial fitting of periodic ripples does not lead to "fake lines" (probability < ~1%). We then show that the ripples can be characterised in a non-subjective manner via Fourier transforms. A 20 ppb PH3 feature is ~5σ compared to the JCMT baseline-uncertainty, and is distinctive as a narrow perturber of the periodic ripple pattern. The structure of the FT-derived baseline also shows that polynomial fitting, if unguided, can amplify artefacts and so artificially reduce significance of real lines.

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arXiv2020

Re-analysis of Phosphine in Venus' Clouds

We first respond to two points raised by Villanueva et al. We show the JCMT discovery spectrum of PH3 can not be re-attributed to SO2, as the line width is larger than observed for SO2 features, and the required abundance would be an extreme outlier. The JCMT spectrum is also consistent with our simple model, constant PH3-abundance with altitude, with no discrepancy in line profile (within data limits); reconciliation with a full photochemical model is the subject of future work. Section 2 presents initial results from re-processed ALMA data. Villanueva et al. noted an issue with bandpass calibration. They have worked on a partially re-processed subset of the ALMA data, so we note where their conclusions, and those of Greaves et al., are now superseded. To summarise: we recover PH3 in Venus' atmosphere with ALMA (~5σ confidence). Localised abundance appears to peak at ~5-10 parts-per-billion (ppb), with suggestions of spatial variation. Advanced data-products suggest a planet-averaged PH3 abundance ~1-4 ppb, lower than from the earlier ALMA processing (which indicated 7+ ppb). The ALMA data are reconcilable with the JCMT detection (~20 ppb) if there is order-of-magnitude temporal variation; more advanced processing of the JCMT data is underway to check methods. Independent PH3 measurements suggest possible altitude dependence (under ~5 ppb at 60+ km, up to ~100 ppb at 50+ km; see Section 2: Conclusions.). Given that both ALMA and JCMT were working at the limit of observatory capabilities, new spectra should be obtained. The ALMA data in-hand are no longer limited by calibration, but spectral ripples still exist, probably due to size and brightness of Venus in relation to the primary beam. Further, spatial ripples are present, potentially reducing significance of real narrow spectral features.

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arXiv2020

Phosphine Gas in the Cloud Decks of Venus

Measurements of trace-gases in planetary atmospheres help us explore chemical conditions different to those on Earth. Our nearest neighbor, Venus, has cloud decks that are temperate but hyper-acidic. We report the apparent presence of phosphine (PH3) gas in Venusian atmosphere, where any phosphorus should be in oxidized forms. Single-line millimeter-waveband spectral detections (quality up to ~15 sigma) from the JCMT and ALMA telescopes have no other plausible identification. Atmospheric PH3 at ~20 parts-per-billion abundance is inferred. The presence of phosphine is unexplained after exhaustive study of steady-state chemistry and photochemical pathways, with no currently-known abiotic production routes in Venusian atmosphere, clouds, surface and subsurface, or from lightning, volcanic or meteoritic delivery. Phosphine could originate from unknown photochemistry or geochemistry, or, by analogy with biological production of phosphine 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.

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arXiv2020

Can Volcanism Build Hydrogen-Rich Early Atmospheres?

Hydrogen in rocky planet atmospheres has been invoked in arguments for extending the habitable zone via N2-H2 and CO2-H2 greenhouse warming, and providing atmospheric conditions suitable for efficient production of prebiotic molecules. On Earth and Super-Earth-sized bodies, where H2-rich primordial envelopes are quickly lost to space, volcanic outgassing can act as a hydrogen source, provided it balances with the loss rate from the top of the atmosphere. Here, we show that both Earth-like and Mars-like planets can sustain atmospheric H2 fractions of several percent across relevant magmatic fO2 ranges. In general this requires hydrogen escape to operate somewhat less efficiently than the diffusion limit. We use a thermodynamical model of magma degassing to determine which combinations of magma oxidation, volcanic flux, and hydrogen escape efficiency can build up appreciable levels of hydrogen in a planet's secondary atmosphere. On a planet similar to the Archean Earth and with a similar magmatic fO2, we suggest that the mixing ratio of atmospheric hydrogen could have been in the range 0.2-3%. A planet erupting magmas around the Iron-Wustite (IW) buffer (i.e., ~3 log fO2 units lower than Archean Earth's), but with otherwise similar volcanic fluxes and H2 loss rates to early Earth, could sustain an atmosphere with approximately 10-20% H2. For an early Mars-like planet with magmas around IW, but a lower range of surface pressures and volcanic fluxes compared to Earth, an atmospheric H2 mixing ratio of 2-8% is possible. On early Mars, this H2 mixing ratio could be sufficient to deglaciate the planet. However, the sensitivity of these results to primary magmatic water contents and volcanic fluxes show the need for improved constraints on the crustal recycling efficiency and mantle water contents of early Mars.

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