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Phosphine on Venus Cannot be Explained by Conventional Processes

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 Added by Janusz Petkowski
 Publication date 2020
  fields Physics
and research's language is English




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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 planets 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 PH3s 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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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 ~5{sigma} 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.
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 (~5{sigma} 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.
The detection of phosphine (PH3) in the atmosphere of Venus has been recently reported based on millimeter-wave radio observations (Greaves et al. 2020), and its re-analyses (Greaves et al. 2021a/b). In this Matters Arising we perform an independent reanalysis, identifying several issues in the interpretation of the spectroscopic data. As a result, we determine sensitive upper-limits for PH3 in Venus atmosphere (>75 km, above the cloud decks) that are discrepant with the findings in G2020 and G2021a/b. The measurements target the fundamental first rotational transition of PH3 (J=1-0) at 266.944513 GHz, which was observed with the James Clerk Maxwell Telescope (JCMT) in June 2017 and with the Atacama Large Millimeter/submillimeter Array (ALMA) in March 2019. This lines center is near the SO2 (J=309,21-318,24) transition at 266.943329 GHz (only 1.3 km/s away from the PH3 line) which represents a potential source of contamination. The JCMT and ALMA data, as presented in G2020, are at spectral resolutions comparable to the frequency separation of the two lines. Moreover, the spectral features identified are several km/s in width, and therefore do not permit distinct spectroscopic separation of the candidate spectral lines of PH3 and SO2. We present the radiative transfer modelling we have performed and then discuss the ALMA and JCMT analyses in turn.
We recover PH3 in the atmosphere of Venus in data taken with ALMA, using three different calibration methods. The whole-planet signal is recovered with 5.4{sigma} confidence using Venus bandpass self-calibration, and two simpler approaches are shown to yield example 4.5-4.8{sigma} detections of the equatorial belt. Non-recovery by Villanueva et al. is attributable to (a) including areas of the planet with high spectral-artefacts and (b) retaining all antenna baselines which raises the noise by a factor ~2.5. We release a data-processing script that enables our whole-planet result to be reproduced. The JCMT detection of PH3 remains robust, with the alternative SO2 attribution proposed by Villanueva et al. appearing inconsistent both in line-velocity and with millimetre-wavelength SO2 monitoring. SO2 contamination of the ALMA PH3-line is minimal. Net abundances for PH3, in the gas column above ~55 km, are up to ~20 ppb planet-wide with JCMT, and ~7 ppb with ALMA (but with signal-loss possible on scales approaching planetary size). Derived abundances will differ if PH3 occupies restricted altitudes - molecules in the clouds will contribute significantly less absorption at line-centre than equivalent numbers of mesospheric molecules - but in the latter zone, PH3 lifetime is expected to be short. Given we recover phosphine, we suggest possible solutions (requiring substantial further testing): a small collisional broadening coefficient could give narrow lines from lower altitude, or a high eddy diffusion coefficient could allow molecules to survive longer at higher altitudes. Alternatively, PH3 could be actively produced by an unknown mechanism in the mesosphere, but this would need to be in addition to cloud-level PH3 detected retrospectively by Pioneer-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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