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Hydrogen chloride (HCl)—a key marker of the chlorine cycle on Mars—has been recently discovered in the Martian atmosphere by the ExoMars/TGO mission. In-orbit data indicate that this molecule appears in the atmosphere only in a limited time period and specifically in the southern summer season. A snapshot global mapping of HCl is indispensable to examine its sources and sinks, but such observations are not currently possible from any orbiters. Here, we present the first spatially resolved map of HCl obtained with the ground-based NASA InfraRed Telescope Facility. We find clear features of HCl, demonstrating that HCl is present close to the surface. HCl is detected in the equatorial region for the first time, revealing that HCl is widely distributed on Mars. However, the spatial distribution of HCl is not uniform, and it is enhanced in the southern polar region. Interestingly, this nonuniform spatial distribution of HCl column abundance is strikingly similar to that of water vapor column abundance. This highlights the important role of water vapor in the evolution of HCl through the atmosphere, as previously noted, and suggests its potential involvement in the atmospheric chlorine source processes.

The stratosphere is thought to play a central role in the atmospheric response to solar irradiance variability. Recent observations suggest that the spectral solar irradiance (SSI) variability involves significant time-dependent spectral variations, with variable degrees of correlation between wavelengths, and new reconstructions are being developed. In this paper, we propose a simplified modelling framework to characterise the effect of short term SSI variability on stratospheric ozone. We focus on the pure photochemical effect, for it is the best constrained one. The photochemical effect is characterised using an ensemble simulation approach with multiple linear regression analysis. A photochemical column model is used with interactive photolysis for this purpose. Regression models and their coefficients provide a characterisation of the stratospheric ozone response to SSI variability and will allow future inter-comparisons between different SSI reconstructions. As a first step in this study, and to allow comparison with past studies, we take the representation of SSI variability from the Lean (1997) solar minimum and maximum spectra. First, solar maximum-minimum response is analysed for all chemical families and partitioning ratios, and is compared with past studies. The ozone response peaks at 0.18 ppmv (approximately 3%) at 37 km altitude. Second, ensemble simulations are regressed following two linear models. In the simplest case, an adjusted coefficient of determination R2 larger than 0.97 is found throughout the stratosphere using two predictors, namely the previous day's ozone perturbation and the current day's solar irradiance perturbation. A better accuracy (R2 larger than 0.9992) is achieved with an additional predictor, the previous day's solar irradiance perturbation. The regression models also provide simple parameterisations of the ozone perturbation due to SSI variability. Their skills as proxy models are evaluated independently against the photochemistry column model. The bias and RMS error of the best regression model are found smaller than 1% and 15% of the ozone response, respectively. Sensitivities to initial conditions and to magnitude of the SSI variability are also discussed.

The record-breaking major stratospheric warming of northern winter 2009 (January–February) is studied using BASCOE (Belgian Assimilation System for Chemical ObsErvation) stratospheric water vapour analyses and MLS (Microwave Limb Sounder) water vapour observations, together with meteorological data from the European Centre for Medium-Range Weather Forecasts (ECMWF) and potential vorticity (PV) derived from ECMWF meteorological data. We focus on the interaction between the cyclonic wintertime stratospheric polar vortex and subsidiary anticyclonic stratospheric circulations during the build-up, peak and aftermath of the major warming. We show dynamical consistency between the water vapour analysed fields and the meteorological and PV fields. Using various approaches, we use the analysed water vapour fields to estimate descent in the polar vortex during this period of between ~0.5 km day−1 and ~0.7 km day−1. New results include the analysis of water vapour during the major warming and demonstration of the benefit of assimilating MLS satellite data into the BASCOE model.

This paper discusses the global analyses of stratospheric ozone (O3) and nitrogen dioxide (NO2) obtained by the Belgian Assimilation System for Chemical Observations from Envisat (BASCOE). Based on a chemistry transport model (CTM) and the 4-dimensional variational (4D-Var) method, BASCOE has assimilated chemical observations of O3, NO2, HNO3, N2O, CH4 and H2O, made between July 2002 and March 2004 by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) onboard the European Space Agency (ESA) Environment Satellite (ENVISAT). This corresponds to the entire period during which MIPAS was operating at its nominal resolution. Our analyses are evaluated against assimilated MIPAS data and independent HALOE (HALogen Occultation Experiment) and POAM-III (Polar Ozone and Aerosol Measurement) satellite data. A good agreement is generally found between the analyses and these datasets, in both cases within the estimated error bars of the observations. The benefit of data assimilation is also evaluated by comparing a BASCOE free model run with MIPAS observations. For O3, the gain from the assimilation is significant during ozone hole conditions, and in the lower stratosphere. Elsewhere, the assimilation does not provide significant improvement. For NO2, the gain from the assimilation is realized through most of the stratosphere. Using the BASCOE analyses, we estimate the differences between MIPAS data and independent data from HALOE and POAM-III, and find results close to those obtained by classical validation methods involving only direct measurement-to-measurement comparisons. Our results extend and reinforce previous MIPAS data validation efforts by taking into account a much larger variety of atmospheric states and measurement conditions. This study discusses possible further developments of the BASCOE data assimilation system; these concern the horizontal resolution, a better filtering of NO2 observations, and the photolysis calculation near the lid of the model. The ozone analyses are part of the PROMOTE project and are publicly available via the BASCOE website (http://www.bascoe.oma.be/promote/).

This study analyzes H 2 O and HDO vertical profiles in the Venus mesosphere using Venus Express/Solar Occultation in the InfraRed data. The findings show increasing H 2 O and HDO volume mixing ratios with altitude, with the D/H ratio rising significantly from 0.025 at ~70 km to 0.24 at ~108 km. This indicates an increase from 162 to 1,519 times the Earth's ratio within 40 km. The study explores two hypotheses for these results: isotopic fractionation from photolysis of H 2 O over HDO or from phase change processes. The latter, involving condensation and evaporation of sulfuric acid aerosols, as suggested by previous authors [X. Zhang et al. , Nat. Geosci. 3, 834-837 (2010)], aligns more closely with the rapid changes observed. Vertical transport computations for H 2 O, HDO, and aerosols show water vapor downwelling and aerosols upwelling. We propose a mechanism where aerosols form in the lower mesosphere due to temperatures below the water condensation threshold, leading to deuterium-enriched aerosols. These aerosols ascend, evaporate at higher temperatures, and release more HDO than H 2 O, which are then transported downward. Moreover, this cycle may explain the SO 2 increase in the upper mesosphere observed above 80 km. The study highlights two crucial implications. First, altitude variation is critical to determining the Venus deuterium and hydrogen reservoirs. Second, the altitude-dependent increase of the D/H ratio affects H and D escape rates. The photolysis of H 2 O and HDO at higher altitudes releases more D, influencing long-term D/H evolution. These findings suggest that evolutionary models should incorporate altitude-dependent processes for accurate D/H fractionation predictions., Competing Interests: Competing interests statement:The authors declare no competing interest.

Isotopic ratios and, in particular, the water D/H ratio are powerful tracers of the evolution and transport of water on Mars. From measurements performed with ExoMars/NOMAD, we observe marked and rapid variability of the D/H along altitude on Mars and across the whole planet. The observations (from April 2018 to April 2019) sample a broad range of events on Mars, including a global dust storm, the evolution of water released from the southern polar cap during southern summer, the equinox phases, and a short but intense regional dust storm. In three instances, we observe water at very high altitudes (>80 km), the prime region where water is photodissociated and starts its escape to space. Rayleigh distillation appears the be the driving force affecting the D/H in many cases, yet in some instances, the exchange of water reservoirs with distinctive D/H could be responsible., (Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

The detection of methane on Mars has been interpreted as indicating that geochemical or biotic activities could persist on Mars today 1 . A number of different measurements of methane show evidence of transient, locally elevated methane concentrations and seasonal variations in background methane concentrations 2-5 . These measurements, however, are difficult to reconcile with our current understanding of the chemistry and physics of the Martian atmosphere 6,7 , which-given methane's lifetime of several centuries-predicts an even, well mixed distribution of methane 1,6,8 . Here we report highly sensitive measurements of the atmosphere of Mars in an attempt to detect methane, using the ACS and NOMAD instruments onboard the ESA-Roscosmos ExoMars Trace Gas Orbiter from April to August 2018. We did not detect any methane over a range of latitudes in both hemispheres, obtaining an upper limit for methane of about 0.05 parts per billion by volume, which is 10 to 100 times lower than previously reported positive detections 2,4 . We suggest that reconciliation between the present findings and the background methane concentrations found in the Gale crater 4 would require an unknown process that can rapidly remove or sequester methane from the lower atmosphere before it spreads globally.

Global dust storms on Mars are rare 1,2 but can affect the Martian atmosphere for several months. They can cause changes in atmospheric dynamics and inflation of the atmosphere 3 , primarily owing to solar heating of the dust 3 . In turn, changes in atmospheric dynamics can affect the distribution of atmospheric water vapour, with potential implications for the atmospheric photochemistry and climate on Mars 4 . Recent observations of the water vapour abundance in the Martian atmosphere during dust storm conditions revealed a high-altitude increase in atmospheric water vapour that was more pronounced at high northern latitudes 5,6 , as well as a decrease in the water column at low latitudes 7,8 . Here we present concurrent, high-resolution measurements of dust, water and semiheavy water (HDO) at the onset of a global dust storm, obtained by the NOMAD and ACS instruments onboard the ExoMars Trace Gas Orbiter. We report the vertical distribution of the HDO/H 2 O ratio (D/H) from the planetary boundary layer up to an altitude of 80 kilometres. Our findings suggest that before the onset of the dust storm, HDO abundances were reduced to levels below detectability at altitudes above 40 kilometres. This decrease in HDO coincided with the presence of water-ice clouds. During the storm, an increase in the abundance of H 2 O and HDO was observed at altitudes between 40 and 80 kilometres. We propose that these increased abundances may be the result of warmer temperatures during the dust storm causing stronger atmospheric circulation and preventing ice cloud formation, which may confine water vapour to lower altitudes through gravitational fall and subsequent sublimation of ice crystals 3 . The observed changes in H 2 O and HDO abundance occurred within a few days during the development of the dust storm, suggesting a fast impact of dust storms on the Martian atmosphere.

Recent measurements of methane (CH 4 ) by the Mars Science Laboratory (MSL) now confront us with robust data that demand interpretation. Thus far, the MSL data have revealed a baseline level of CH 4 (∼0.4 parts per billion by volume [ppbv]), with seasonal variations, as well as greatly enhanced spikes of CH 4 with peak abundances of ∼7 ppbv. What do these CH 4 revelations with drastically different abundances and temporal signatures represent in terms of interior geochemical processes, or is martian CH 4 a biosignature? Discerning how CH 4 generation occurs on Mars may shed light on the potential habitability of Mars. There is no evidence of life on the surface of Mars today, but microbes might reside beneath the surface. In this case, the carbon flux represented by CH 4 would serve as a link between a putative subterranean biosphere on Mars and what we can measure above the surface. Alternatively, CH 4 records modern geochemical activity. Here we ask the fundamental question: how active is Mars, geochemically and/or biologically? In this article, we examine geological, geochemical, and biogeochemical processes related to our overarching question. The martian atmosphere and surface are an overwhelmingly oxidizing environment, and life requires pairing of electron donors and electron acceptors, that is, redox gradients, as an essential source of energy. Therefore, a fundamental and critical question regarding the possibility of life on Mars is, "Where can we find redox gradients as energy sources for life on Mars?" Hence, regardless of the pathway that generates CH 4 on Mars, the presence of CH 4 , a reduced species in an oxidant-rich environment, suggests the possibility of redox gradients supporting life and habitability on Mars. Recent missions such as ExoMars Trace Gas Orbiter may provide mapping of the global distribution of CH 4 . To discriminate between abiotic and biotic sources of CH 4 on Mars, future studies should use a series of diagnostic geochemical analyses, preferably performed below the ground or at the ground/atmosphere interface, including measurements of CH 4 isotopes, methane/ethane ratios, H 2 gas concentration, and species such as acetic acid. Advances in the fields of Mars exploration and instrumentation will be driven, augmented, and supported by an improved understanding of atmospheric chemistry and dynamics, deep subsurface biogeochemistry, astrobiology, planetary geology, and geophysics. Future Mars exploration programs will have to expand the integration of complementary areas of expertise to generate synergistic and innovative ideas to realize breakthroughs in advancing our understanding of the potential of life and habitable conditions having existed on Mars. In this spirit, we conducted a set of interdisciplinary workshops. From this series has emerged a vision of technological, theoretical, and methodological innovations to explore the martian subsurface and to enhance spatial tracking of key volatiles, such as CH 4 .

The authors propose a new method, the Helfand-moment method, to compute the shear viscosity by equilibrium molecular dynamics in periodic systems. In this method, the shear viscosity is written as an Einstein-type relation in terms of the variance of the so-called Helfand moment. This quantity is modified in order to satisfy systems with periodic boundary conditions usually considered in molecular dynamics. They calculate the shear viscosity in the Lennard-Jones fluid near the triple point thanks to this new technique. They show that the results of the Helfand-moment method are in excellent agreement with the results of the standard Green-Kubo method.

The thermal conductivity is calculated with the Helfand-moment method in the Lennard-Jones fluid near the triple point. The Helfand moment of thermal conductivity is here derived for molecular dynamics with periodic boundary conditions. Thermal conductivity is given by a generalized Einstein relation with this Helfand moment. The authors compute thermal conductivity by this new method and compare it with their own values obtained by the standard Green-Kubo method. The agreement is excellent.

We apply the escape-rate formalism to compute the shear viscosity in terms of the chaotic properties of the underlying microscopic dynamics. A first-passage problem is set up for the escape of the Helfand moment associated with viscosity out of an interval delimited by absorbing boundaries. At the microscopic level of description, the absorbing boundaries generate a fractal repeller. The fractal dimensions of this repeller are directly related to the shear viscosity and the Lyapunov exponent, which allows us to compute its values. We apply this method to the Bunimovich-Spohn minimal model of viscosity which is composed of two hard disks in elastic collision on a torus. These values are in excellent agreement with the values obtained by other methods such as the Green-Kubo and Einstein-Helfand formulas.

We report a study of viscosity by the method of Helfand moment in systems with periodic boundary conditions. We propose a new definition of Helfand moment which takes into account the minimum image convention used in molecular dynamics with periodic boundary conditions. Our Helfand-moment method is equivalent to the method based on the Green-Kubo formula and is not affected by ambiguities due to the periodic boundary conditions. Moreover, in hard-ball systems, our method is equivalent to that developed by Alder, Gass, and Wainwright [J. Chem. Phys. 53, 3813 (1970)]. We apply and verify our method in a fluid composed of N> or =2 hard disks in elastic collisions. We show that the viscosity coefficients already take values in good agreement with Enskog's theory for N=2 hard disks in a hexagonal geometry.