Abiotic chemical routes towards the phosphine synthesis in the atmosphere of Venus

(2022)

Authors:

Martin Ferus, Giuseppe Cassone, Paul Rimmer, Franz Saija, Klaudia Mráziková, Antonín Knížek, Svatopluk Civiš

Abstract:

<p>Several of the Venera, Vega and Pioneer probe data as well as ground based observation support the presence of so-called Redox Disequilibrium Pairs (RDPs) in atmosphere of so hostile world as Venus (Greaves 2021). State of the art chemical networks cannot explain origin of an important RDP, phosphine, in oxidized atmosphere of Venus by a conventional processes (Bains 2021). We used the hybrid Density Functional Theory (DFT) for investigation of a series of chemical reaction pathways leading to the reduction of phosphate monoxide to phosphine. Our calculations indicated that a reaction network similar to photochemical synthesis of methane from carbon monoxide over acidic surfaces suggested for Mars (Civiš 2019) can also occur in clouds of Venus. As a seminal step, we have explored – via state-of-the-art quantum-based calculations – the a priori energetic feasibility of the following reaction:</p><p>HCO(radical) + PO = CO2 + PH (biradical).</p><p>Our calculations have shown that chemical conversion is constituted of three steps. Two of them are energetically favoured, however, the final conversion to phosphine is hardened by a significant activation barrier. This barrier can be overcome by a reaction of OPH radical with hydrogen radical. For assessing the potential of the newly introduced reaction mechanisms, models of the Venus and early Earth atmospheres in ARGO code and modified STAND chemical network were created and verified. Comparison of reaction yields suggests that this pathway is potentially effective enough and could be the source of phosphine recently discovered on Venus. </p><p>We acknowledge the support provided by the Czech Science Foundation within the project reg. no. 21-11366S and by ERDF/ESF "Centre of Advanced Applied Sciences" (No. CZ.02.1.01/0.0/0.0/16_019/0000778). We acknowledge support of the Czech Academy of Sciences, Strategy AV21, project VP16. The Czech team is part of the VenSpec-H Consortium onboard the ESA EnVision mission.</p><p>References:</p><p>Civiš S. et al.: Formation of Methane and (Per)Chlorates on Mars. ACS Earth Space Chem. 2019, 3, 2, 221–232.</p><p>Bains W. et al.: Phosphine on Venus Cannot Be Explained by Conventional Processes. Astrobiology 2021, 10 (21), 1277-1304.</p><p>Greaves J. S. et al.:  Phosphine gas in the cloud decks of Venus. Nature Astronomy 2021, 5, 655–664.</p>

The stability of benzene in planetary atmospheres

(2022)

Authors:

Antonín Knížek, Lukáš Petera

Abstract:

<p>Benzene is the simplest organic compound with a 6-carbon aromatic ring. As such, it was used as a first order representative of aromatic compounds in planetary atmospheres. These compounds can be brought by asteroid impacts into rocky planetary atmospheres, where they can serve as precursors for further synthesis. Our experiments show that benzene vapours in nitrogen-dominated atmospheres subjected to asteroid impacts (modelled by laboratory laser shots) lead to the formation of acetylene and hydrogen cyanide. Both these products appear in many proposed mechanisms of prebiotic chemistry.</p>

Uncertainty in aerosol-cloud radiative forcing is driven by clean conditions

(2022)

Authors:

Edward Gryspeerdt, Adam C Povey, Roy G Grainger, Otto Hasekamp, N Christina Hsu, Jane P Mulcahy, Andrew M Sayer, Armin Sorooshian

Is anthropogenic global warming accelerating?

Journal of Climate American Meteorological Society 35:24 (2022) 4273-4290

Authors:

Stuart Jenkins, Adam Povey, Andrew Gettelman, Roy Grainger, Philip Stier, Myles Allen

Abstract:

Estimates of the anthropogenic effective radiative forcing (ERF) trend have increased by 50% since 2000 (+0.4W/m2/decade in 2000-2009 to +0.6W/m2/decade in 2010-2019), the majority of which is driven by changes in the aerosol ERF trend, due to aerosol emissions reductions. Here we study the extent to which observations of the climate system agree with these ERF assumptions. We use a large ERF ensemble from IPCC’s Sixth Assessment Report (AR6) to attribute the anthropogenic contributions to global mean surface temperature (GMST), top-of-atmosphere radiative flux, and aerosol optical depth observations. The GMST trend has increased from +0.18°C/decade in 2000-2009 to +0.35°C/decade in 2010-2019, coinciding with the anthropogenic warming trend rising from +0.19°C/decade in 2000-2009 to +0.24°C/decade in 2010-2019. This, and observed trends in top-of-atmosphere radiative fluxes and aerosol optical depths support the claim of an aerosol-induced temporary acceleration in the rate of warming. However, all three observation datasets additionally suggest smaller aerosol ERF trend changes are compatible with observations since 2000, since radiative flux and GMST trends are significantly influenced by internal variability over this period. A zero-trend-change aerosol ERF scenario results in a much smaller anthropogenic warming acceleration since 2000, but is poorly represented in AR6’s ERF ensemble. Short-term ERF trends are difficult to verify using observations, so caution is required in predictions or policy judgments that depend on them, such as estimates of current anthropogenic warming trend, and the time remaining to, or the outstanding carbon budget consistent with, 1.5°C warming. Further systematic research focused on quantifying trends and early identification of acceleration or deceleration is required.

Quantifying the impact of meteorological uncertainty on emission estimates and the risk to aviation using source inversion for the Raikoke 2019 eruption

Atmospheric Chemistry and Physics European Geosciences Union 22:13 (2022) 8529-8545

Abstract:

Due to the remote location of many volcanoes, there is substantial uncertainty about the timing, amount and vertical distribution of volcanic ash released when they erupt. One approach to determine these properties is to combine prior estimates with satellite retrievals and simulations from atmospheric dispersion models to create posterior emission estimates, constrained by both the observations and the prior estimates, using a technique known as source inversion. However, the results are dependent not only on the accuracy of the prior assumptions, the atmospheric dispersion model and the observations used, but also on the accuracy of the meteorological data used in the dispersion simulations. In this study, we advance the source inversion approach by using an ensemble of meteorological data from the Met Office Global and Regional Ensemble Prediction System to represent the uncertainty in the meteorological data and apply it to the 2019 eruption of Raikoke. Retrievals from the Himawari-8 satellite are combined with NAME dispersion model simulations to create posterior emission estimates. The use of ensemble meteorology provides confidence in the posterior emission estimates and associated dispersion simulations that are used to produce ash forecasts. Prior mean estimates of fine volcanic ash emissions for the Raikoke eruption based on plume height observations are more than 15 times higher than any of the mean posterior ensemble estimates. In addition, the posterior estimates have a different vertical distribution, with 27 %–44 % of ash being emitted into the stratosphere compared to 8 % in the mean prior estimate. This has consequences for the long-range transport of ash, as deposition to the surface from this region of the atmosphere happens over long timescales. The posterior ensemble spread represents uncertainty in the inversion estimate of the ash emissions. For the first 48 h following the eruption, the prior ash column loadings lie outside an estimate of the error associated with a set of independent satellite retrievals, whereas the posterior ensemble column loadings do not. Applying a risk-based methodology to an ensemble of dispersion simulations using the posterior emissions shows that the area deemed to be of the highest risk to aviation, based on the fraction of ensemble members exceeding predefined ash concentration thresholds, is reduced by 49 %. This is compared to estimates using an ensemble of dispersion simulations using the prior emissions with ensemble meteorology. If source inversion had been used following the eruption of Raikoke, it would have had the potential to significantly reduce disruptions to aviation operations. The posterior inversion emission estimates are also sensitive to uncertainty in other eruption source parameters and internal dispersion model parameters. Extending the ensemble inversion methodology to account for uncertainty in these parameters would give a more complete picture of the emission uncertainty, further increasing confidence in these estimates.