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Odd-hydrogen (HO |$_\mathrm{x}$|⁠) species have a crucial role in regulating the chemistry of the atmosphere of Mars and are important to understand some of the most fundamental aspects regarding its atmospheric composition such as the long-term stability of CO |$_2$|⁠. Despite the key role of these species for our understanding of the Martian photochemistry, there is little observational evidence constraining their abundances. In this study, we use infrared solar occultation observations from the Atmospheric Chemistry Suite aboard the ExoMars Trace Gas Orbiter to search for spectral signatures of HO |$_2$| in the atmosphere of Mars. In our analysis of the data, we retrieve vertical profiles of pressure, temperature, and water vapour mixing ratio, but are unable to confidently detect the presence of HO |$_2$| features in the spectra. We report upper limits of 15 ppbv (5 |$\sigma$|⁠), which represents an order of magnitude improvement with respect to previous investigations. Comparing the derived upper limits with the expectations from 3-dimensional Global Climate Models, we find that approximately an order of magnitude improvement in the instrument sensitivity would be required to detect this molecule and/or constrain the models. [ABSTRACT FROM AUTHOR]

On Mars, condensation is the major factor constraining the vertical distribution of water vapor. Recent measurements of water and temperature profiles showed that water can be strongly supersaturated at and above the level where clouds form during the aphelion and perihelion seasons. Since 2018, the near‐infrared spectrometer (NIR) of the Atmospheric Chemistry Suite onboard the Trace Gas Orbiter has measured H2O and temperature profiles using solar occultation in the infrared from below 10 to 100 km of altitude. Here, we provide the first long‐term monitoring of the water saturation state. The survey spans 2 Martian years from Ls = 163° of MY34 to Ls = 170° of MY36. We found that water is often supersaturated above aerosol layers. In the aphelion season, the water mixing ratio above 40 km in the mid‐to‐high latitudes was below 3 ppmv and yet is found to be supersaturated. Around the perihelion, water is also supersaturated above 60 km with a mixing ratio of 30–50 ppmv. Stronger saturation is observed during the dusty season in MY35 compared to what was observed in MY34 during the Global Dust Storm and around the perihelion. Saturation varied between the evening and morning terminators in response to temperature modulation imparted by thermal tides. Although water vapor is more abundant in the evening, colder morning temperatures induce a daily peak of saturation. This data set establishes a new paradigm for water vapor on Mars, revealing that supersaturation is nearly ubiquitous, particularly during the dust season, thereby promoting water escape on an annual average. Plain Language Summary: The rate of water loss from Mars depends on hydrogen, the main product of the H2O photodissociation escaping from the upper atmosphere. The ability of water to reach high altitudes and to be a direct source of atomic hydrogen is limited by cloud formation, which holds water vapor in the lower atmosphere. This process is regulated by temperature and pressure. Condensation starts when the temperature is cold enough and condensation nuclei (CN) (e.g., small dust particles) are available. If CN are lacking, or their sizes are too small, or the temperature drops too fast, then water vapor becomes supersaturated. Recent studies have shown that Martian water vapor is often supersaturated. Here, we present the first seasonal cycle of the saturation state from simultaneous measurements of water and temperature during two Martian years by Atmospheric Chemistry Suite on the Trace Gas Orbiter. Our results show that supersaturation is typical on Mars. It occurs above clouds both in the aphelion and perihelion seasons as well as in the lower polar atmosphere. We demonstrate supersaturation to be an important factor facilitating the escape of water. Unlike the Earth, water easily penetrates the upper atmosphere and reaches photodissociation altitudes. Key Points: Long‐term observations of H2O saturation state in the atmosphere of Mars show that supersaturation is nearly ubiquitous above aerosol layersDuring the dusty season, the supersaturation is stronger in MY35 compared to MY34More water was found in the evening terminator and stronger supersaturation in the morning terminator [ABSTRACT FROM AUTHOR]

Carbon monoxide is a non‐condensable gas in the Martian atmosphere produced by the photolysis of CO2. Its abundance responds to the condensation and sublimation of CO2 from the polar caps, resulting in seasonal variations of the CO mixing ratio. ACS onboard the ExoMars Trace Gas Orbiter have measured CO in infrared bands by solar occultation. Here we provide the first long‐term monitoring of the CO vertical distribution at the altitude range from 0 to 80 km for 1.5 Martian years from Ls = 163° of MY34 to the end of MY35. We obtained a mean CO mixing ratio of ∼960 ppmv at latitudes from 45°S to 45°N and altitudes below 40 km, mostly consistent with previous observations. We found a strong enrichment of CO near the surface at Ls = 100–200° in high southern latitudes with a layer of 3,000–4,000 ppmv, corresponding to local depletion of CO2. At equinoxes we found an increase of the CO mixing ratio above 50 km to 3,000–4,000 ppmv at high latitudes of both hemispheres explained by the downwelling flux of the Hadley circulation on Mars, which drags the CO enriched air. General circulation models tend to overestimate the intensity of this process, bringing too much CO. The observed minimum of CO in the high and mid‐latitudes southern summer atmosphere amounts to 700–750 ppmv, agreeing with nadir measurements. During the global dust storm of MY34, when the H2O abundance peaks, we see less CO than during the calm MY35, suggesting an impact of HOx chemistry on the CO abundance. Plain Language Summary: Carbon monoxide (CO) is a product of the photodissociation of the main component of the Martian atmosphere, CO2 (96%). During the polar night on Mars, the temperature drops so low that ∼30% of the global atmospheric carbon dioxide freezes out, condensed into snowflakes. They settle to the ground to form a seasonal polar cap, which sublimates in spring. Unlike CO2, CO is not a condensable species, so its relative abundance increases when CO2 and the atmospheric pressure drops, forming a prominent seasonal cycle. This behavior of CO was well documented by spacecraft measurements of column abundances, while its vertical distribution remained poorly known until recently. Still, it helps to separate the impacts of atmospheric dynamics and chemistry, addressing the problem of the Martian atmosphere's stability. We present the first climatology of the CO vertical distribution lasting more than one Martian year based on solar occultations by the ExoMars Trace Gas Orbiter. We report a previously unobserved CO layer near the surface in high southern latitudes in late winter and spring and document the difference between two Martian years caused by the global dust storm. These observations give new challenges to General Circulation Models for understanding the modern atmosphere of Mars. Key Points: The first climatology of CO vertical profiles is collected for the period Ls = 163° of Martian Year 34 to the end of Martian Year 35The mean CO volume mixing ratio is ∼960 ppmv at 0–35 km and 45°S–45°NStrong enrichment of CO, >3,000 ppmv, is detected at 10–20 km at Ls = 100–200 in high southern latitudes and above 50 km at equinoxes near Poles [ABSTRACT FROM AUTHOR]

Isotopic ratios in atmospheric CO2 are shaped by various processes throughout Mars' history, and can help understand what the atmosphere of early Mars was like to sustain liquid water on its surface. In this study, we monitor the O and C isotopic composition of CO2 between 70 and 130 km for more than half a Martian year using solar occultation observations by the Atmospheric Chemistry Suite onboard the ExoMars Trace Gas Orbiter. We find the vertical trends of the isotopic ratios to be consistent with the expectations from diffusive separation above the homopause, with average values below this altitude being consistent with Earth‐like fractionation (δ13C = −3 ± 37‰; δ18O = −29 ± 38‰; and δ17O = −11 ± 41‰). Using these measurements, we estimate that at least 20%–40% of primordial C on Mars has escaped to space throughout history. The total amount of C lost from the atmosphere is likely to be well in excess of this lower limit, due to carbonate formation and further sink processes. In addition, we propose a photochemical transfer of light O from H2O to CO2 to explain the larger enrichment in the O18/O16 ${}^{18}\mathrm{O}/{}^{16}\mathrm{O}$ ratio in H2O than in CO2. Plain Language Summary: There is ample evidence suggesting that liquid water was abundant on the surface of Mars in the past. However, climatic conditions on early Mars must have been very different from the ones we observe today to sustain liquid water on its surface. The ratios of the heavy and light isotopes in different species provide a very useful tool to estimate the early climate of Mars. In this study, we monitor the isotopic ratios of carbon dioxide in the atmosphere of Mars to provide more accurate estimates of these. With our measurements, and in context with previous studies, we estimate that at least 20%–40% of the carbon reservoir has been lost to space throughout Martian history. This, together with the sequestration of atmospheric C on the surface in the form of minerals, is consistent with the idea that the atmosphere of early Mars was denser than the one we observe today. Key Points: Isotopic ratios in CO2 are observed to be consistent with telluric standards and to fractionate by diffusive separation above the homopauseAt least 20%–40% of the C reservoir has escaped to space throughout Martian historyThe higher 18O/16O ratio in H2O than in CO2 may be explained by a photochemical transfer of lighter O from H2O to CO2 [ABSTRACT FROM AUTHOR]

We present the first water vapor profiles encompassing the upper mesosphere of Mars, 100–120 km, far exceeding the maximum altitudes where remote sensing has been able to observe water to date. Our results are based on solar occultation measurements by Atmospheric Chemistry Suite (ACS) onboard the ExoMars Trace Gas Orbiter (TGO). The observed wavelength range around 2.7 μm possesses strong CO2 and H2O absorption lines allowing sensitive temperature and density retrievals. We report a maximum H2O mixing ratio varying from 10 to 50 ppmv at 100–120 km during the global dust storm (GDS) of Martian Year (MY) 34 and around southern summer solstice of MY 34 and 35. During other seasons water remains persistently below ∼2 ppmv. We claim that contributions of the MY34 GDS and perihelion periods into the projected hydrogen escape from Mars are nearly equivalent. Plain Language Summary: We report regular events of high abundances of the water vapor (H2O) in the upper atmosphere of Mars (100–120 km). So far, any water enrichment has not been revealed by remote sensing at such high altitudes. Higher than 80 km, solar light breaks water vapor molecules into H and O atoms, which may reach the exosphere and escape the planet. When Mars is closer to the Sun (the perihelion season), the atmosphere's circulation intensifies, causing increased dust activity with global dust storms (GDS), occurring every 3–4 Mars years. We observed during the second halves of Martian years 34 and 35 (2018–2020), including one GDS and two perihelion seasons. We report that the maximum water relative abundance reaches 10–50 parts per million in volume (ppmv) at 100–120 km during the GDS and every perihelion season. These high values indicate that the Martian atmosphere above 100 km regularly hosts large amounts of water, facilitating the long‐term escape of water from the planet. Key Points: Water abundances are reported in a previously unexplored altitude range: from 100 to 120 kmThe observed GDS (MY34) and two perihelion seasons (MY34, 35) reveal the H2O content around 10–50 parts per million by volume at 100–120 kmContributions of the MY34 GDS and perihelion periods into the projected hydrogen escape from Mars are nearly equivalent [ABSTRACT FROM AUTHOR]

The detection of methane on Mars has been interpreted as indicating that geochemical or biotic activities could persist on Mars today1. A number of different measurements of methane show evidence of transient, locally elevated methane concentrations and seasonal variations in background methane concentrations2–5. These measurements, however, are difficult to reconcile with our current understanding of the chemistry and physics of the Martian atmosphere6,7, which—given methane's lifetime of several centuries—predicts an even, well mixed distribution of methane1,6,8. 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 detections2,4. We suggest that reconciliation between the present findings and the background methane concentrations found in the Gale crater4 would require an unknown process that can rapidly remove or sequester methane from the lower atmosphere before it spreads globally. Highly sensitive measurements of the atmosphere of Mars with the ExoMars Trace Gas Orbiter do not detect any methane over a range of latitudes in both hemispheres, in contrast to previous local or remote detections. [ABSTRACT FROM AUTHOR]

A major quest in Mars' exploration has been the hunt for atmospheric gases, potentially unveiling ongoing activity of geophysical or biological origin. Here, we report the first detection of a halogen gas, HCl, which could, in theory, originate from contemporary volcanic degassing or chlorine released from gas-solid reactions. Our detections made at ~3.2 to 3.8 μm with the Atmospheric Chemistry Suite and confirmed with Nadir and Occultation for Mars Discovery instruments onboard the ExoMars Trace Gas Orbiter, reveal widely distributed HCl in the 1- to 4-ppbv range, 20 times greater than previously reported upper limits. HCl increased during the 2018 global dust storm and declined soon after its end, pointing to the exchange between the dust and the atmosphere. Understanding the origin and variability of HCl shall constitute a major advance in our appraisal of martian geo- and photochemistry., (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).)

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.