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This study analyzes H2O and HDO vertical profiles in the Venus mesosphere using Venus Express/Solar Occultation in the InfraRed data. The findings show increasing H2O 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 H2O 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 H2O, 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 H2O, which are then transported downward. Moreover, this cycle may explain the SO2 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 H2O 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. [ABSTRACT FROM AUTHOR]

Etalons are pairs of parallel plate mirrors with wavelength-scale spacing that exhibit cavity modes, giving transmission maxima (fringes) due to constructive interference. Infrared transmission measurements as a function of angle were used to determine the effective mass of etalon cavity modes using a gap filled with air and then liquid carbon tetrachloride. The air-filled etalon gives results in agreement with pure photon expectations established herein. Liquids with vibrations having strong infrared transition intensity (vibrational strong coupling mode) can strongly perturb the pattern of transmission resonances, creating mixed states of infrared cavity modes and molecular vibrations, i.e., cavity-vibration polaritons. The effective mass of one cavity-vibration polariton close to the strong vibration of carbon tetrachloride is 4.36 times heavier than the pure photon cavity mode expectation, i.e., the mass factor vs pure light. The mass factors are largest when closest to the strong vibrational frequency, and they converge to the one far away from the strong vibration. This work gives quantitative values of the effective mass of cavity-vibration polariton states and is a diagnostic for the mixing of vibrations with etalon transmission. [ABSTRACT FROM AUTHOR]

We present CO density profiles up to about 100 km in the Martian atmosphere obtained for the first time from retrievals of solar occultation measurements by the Nadir and Occultation for Mars Discovery (NOMAD) onboard ExoMars Trace Gas Orbiter (TGO). CO is an important trace gas on Mars, as it is controlled by CO2 photolysis, chemical reaction with the OH radicals, and the global dynamics. However, the measurements of CO vertical profiles have been elusive until the arrival of TGO. We show how the NOMAD CO variations describe very well the Mars general circulation. We observe a depletion of CO in the upper troposphere and mesosphere during the peak period, LS = 190°–200°, more pronounced over the northern latitudes, confirming a similar result recently reported by Atmospheric Chemistry Suite onboard TGO. However, in the lower troposphere around 20 km, and at least at high latitudes of the S. hemisphere, NOMAD CO mixing ratios increase over 1,500 ppmv during the GDS (Global Dust Storm) onset. This might be related to the downwelling branch of the Hadley circulation. A subsequent increase in tropospheric CO is observed during the decay phase of the GDS around LS = 210°–250° when the dust loading is still high. This could be associated with a reduction in the amount of OH radicals in the lower atmosphere due to lack of solar insolation. Once the GDS is over, CO steadily decreases globally during the southern summer season. A couple of distinct CO patterns associated with the Summer solstice and equinox circulation are reported and discussed. Plain Language Summary: CO is an extremely interesting trace species in the Martian atmosphere. It has been used for both dynamical and photochemical studies of the atmosphere. But its vertical distribution has not been systematically measured until the arrival of the Exomars Trace Gas Orbiter (TGO). We use observations of the NOMAD (Nadir and Occultation for Mars Discovery) spectrometer onboard TGO to retrieve full profiles of mixing ratios of CO up to 100 km with a good vertical resolution. The retrievals cover two Martian seasons during which a global dust storm event occurred. We have found the behavior of CO during this event to be governed by local chemistry as well as by the long range transport. During the dust storm, CO mixing ratios are depleted all over the globe while over the southern high latitudes, we discover an increase in CO due to transport from low latitudes during the end of the southern winter. The dynamical effect of global transport is found in the vertical distribution of CO during the southern summer. Another important result, where the local chemistry might be at play is the increase of CO in the low altitudes over low and midlatitudes during the decay phase of the GDS. Key Points: Global map of CO profiles from Nadir and Occultation for Mars Discovery solar occultation observations during the first year of Trace Gas Orbiter operations is presented for the first timeDuring the onset of the 2018 global dust storm (GDS), the CO volume mixing ratios (VMRs) are found to be depleted by 28% at 50 km compared to the average CO VMR valuesHigh CO abundance at tropospheric altitudes is observed over NH during decay of the GDS when the atmospheric dust loading is high [ABSTRACT FROM AUTHOR]

We present vertical profiles of temperature and density from solar occultation (SO) observations by the "Nadir and Occultation for Mars Discovery" (NOMAD) spectrometer on board the Trace Gas Orbiter during its first operational year, which covered the second half of Mars Year 34. We used calibrated transmittance spectra in 380 scans, and apply an in‐house pre‐processing to clean data systematics. Temperature and CO2 profiles up to about 90 km, with consistent hydrostatic adjustment, are obtained, after adapting an Earth‐tested retrieval scheme to Mars conditions. Both pre‐processing and retrieval are discussed to illustrate their performance and robustness. Our results reveal the large impact of the MY34 Global Dust Storm (GDS), which warmed the atmosphere at all altitudes. The large GDS aerosols opacity limited the sounding of tropospheric layers. The retrieved temperatures agree well with global climate models (GCM) at tropospheric altitudes, but NOMAD mesospheric temperatures are wavier and globally colder by 10 K in the perihelion season, particularly during the GDS and its decay phase. We observe a warm layer around 80 km during the Southern Spring, especially in the Northern Hemisphere morning terminator, associated to large thermal tides, significantly stronger than in the GCM. Cold mesospheric pockets, close to CO2 condensation temperatures, are more frequently observed than in the GCM. NOMAD CO2 densities show oscillations upon a seasonal trend that track well the latitudinal variations expected. Results uncertainties and suggestions to improve future data re‐analysis are briefly discussed. Plain Language Summary: The detailed variation of temperature and density with altitude is of paramount importance to characterize the atmospheric state and to constrain the chemistry and dynamics as a whole. The Nadir and Occultation for Mars Discovery (NOMAD) instrument on board the Trace Gas Orbiter (TGO) has among its key targets the characterization of the thermal state with unprecedented vertical resolution. This is the target of this work, where we analyzed transmittance spectra obtained from the NOMAD solar occultation channel, with a state‐of‐the‐art retrieval scheme, adapted from Earth to Mars conditions and geometry. We applied it to the first year of TGO observations, which covered the last two Mars seasons of Mars Year 34. The results permit to study the temperature structure up to 90 km and its seasonal and latitudinal variations, revealing the impact of the MY34 Global Dust Storm, a warm layer at mesospheric altitudes not present in climate models, more frequent cold pockets than in current global climate models, and generally, colder temperature at those altitudes, all of which can be of importance for the validation of these climate models. Key Points: Temperature and density profiles up to 90 km are retrieved from Nadir and Occultation for Mars Discovery (NOMAD) first year of solar occultations, covering two seasons of Mars Year 34NOMAD temperatures agree well with climate model predictions below 50 km but are wavier and globally colder by about 10 K at high altitudesWe report large thermal tides producing warm layers at 80 km in the morning terminator. Also strong warming by the 2018 global dust storm [ABSTRACT FROM AUTHOR]

We report vertical profiles of water and D/H for one Martian year as measured with the TGO/NOMAD instrument. The observations were performed via solar occultation, providing water profiles up to ∼100 km and D/H up to ∼60 km, with a vertical resolution of 1–2 km. The measurements reveal dramatic variability of water and D/H over short timescales and with altitude and location on the planet. We investigated the release of seasonal water from the polar caps during southern and northern summer, by mapping water and its D/H near the polar regions. Above the hygropause, the D/H drops substantially below 2 VSMOW, and both seasonal polar caps show a consistent and enriched D/H of 5–7 VSMOW within the hygrosphere. Plain Language Summary: In our observations of water and its deuterium isotopic ratio (D/H) across a whole Martian year, we observe dramatic variations in the vertical distributions, in particular during dusty storms. The D/H ratio measured above the seasonal northern polar cap is consistent with that above the southern polar cap. Key Points: A full Martian year of water and D/H ratio data are reportedDramatic variations are observed in the vertical distributions of water and D/H during the dusty seasonsThe D/H ratio measured above the seasonal northern polar cap is consistent with that above the southern polar cap [ABSTRACT FROM AUTHOR]

Using the Nadir and Occultation for MArs Discovery instrument aboard Trace Gas Orbiter, we derived the CO/CO2 profiles between 75 and 105 km altitude with the equivalent width technique. The derived CO/CO2 profiles showed significant seasonal variations in the southern hemisphere with decreases near perihelion and increases near aphelion. The estimation of the CO/CO2 profiles with a one‐dimensional photochemical model shows that an altitude‐dependent eddy diffusion coefficient better reproduces the observed profiles than a vertically uniform one. Our estimation suggests that the eddy diffusion coefficient in Ls = 240–270 is uniformly larger by a factor of ∼2 than that in Ls = 90–120 in the southern hemisphere, while they are comparable in the northern hemisphere. This fact demonstrates that the eddy diffusion coefficient is variable with season and latitude. Plain Language Summary: The eddy diffusion coefficient is widely used to parameterize the efficiency of vertical diffusion in the planetary atmosphere, whose variation characterizes the transportation of trace gas species. Additionally, it could vary their vertical distributions in the middle and upper atmosphere, which might cause an impact on the species escaping to space. However, the variability of the eddy diffusion coefficient in those altitude regions have been poorly understood. In this study, we focus on the estimation of variation in the eddy diffusion coefficient by analyzing the CO and CO2 measurements made by the ExoMars Trace Gas Orbiter. The observed CO/CO2 ratio between altitudes of 75 and 105 km shows a significant seasonal variation in the southern hemisphere. The observed CO/CO2 profiles are compared with the simulated profiles obtained with a one‐dimensional photochemical model assigning several shapes and intensity of eddy diffusion coefficient. The comparison shows that the eddy diffusion coefficient is not constant but variable depending on altitude, season, and latitude, which suggests that the efficiency of the vertical diffusion varies with season and latitude. This fact is useful to other 1D photochemical models to reproduce the seasonal and latitudinal variation of atmospheric composition. Key Points: The CO/CO2 profiles from 75 to 105 km measured by NOMAD aboard TGO are used to investigate variations in the eddy diffusion coefficientThe estimated CO/CO2 profiles agree well with the observed profiles if altitude‐dependent eddy diffusion coefficients are consideredOur results demonstrate a substantial seasonal variation in the eddy diffusion coefficient in the southern hemisphere [ABSTRACT FROM AUTHOR]

Following the recent detection of HCl in the atmosphere of Mars by ExoMars/Trace Gas Orbiter, we present here the first measurement of the 37Cl/35Cl isotopic ratio in the Martian atmosphere using a set of Nadir Occultation for MArs Discovery (NOMAD) observations. We determine an isotopic anomaly of −6 ± 78‰ compared to Earth standard, consistent with the −51‰–−1‰ measured on Mars' surface by Curiosity. The measured isotopic ratio is also consistent with surface measurements, and suggests that Cl reservoirs may have undergone limited processing since formation in the Solar Nebula. The examination of possible sources and sinks of HCl shows only limited pathways to short‐term efficient Cl fractionation and many plausible reservoirs of "light" Cl. Plain Language Summary: Recently, HCl has been observed in the Martian atmosphere for the first time by the instruments onboard the European Space Agency (ESA) ExoMars Trace Gas Orbiter. This discovery implies that there is an active chemical and physical cycle of chlorine in the Martian atmosphere. The Cl in HCl is usually present with its two stable main isotopes, the "light" 35Cl and "heavy" 37Cl, their ratio in chlorine‐bearing compounds is variable across the Solar System, and can be revealing of the chemistry at play, surface‐atmosphere interactions and the degree of evolution of chlorine reservoirs. In this work, we measure the 37Cl to 35Cl ratio for the first time in the Martian atmosphere. In average, we find that the measured atmospheric value is slightly "lighter" than the standard value at Earth (although with large uncertainty), and consistent with that measured at Mars' surface. This indicates that Cl does not actively escape from the Martian atmosphere, and that the Cl chemistry at Mars has little efficiency in changing the isotopic signature of Cl, if at all. The "light" Cl isotopic composition of surface and atmosphere may indicate that Cl reservoirs on Mars are less processed than other bodies in the Solar System. Key Points: Cl isotopic ratio in atmospheric HCl on Mars is measured with Nadir Occultation for MArs Discovery (NOMAD), finding a slight depletion of 37Cl compared to Earth standardThe atmospheric Cl isotopic ratio is compatible with surface values measured by Mars Science Laboratory (MSL), not showing any fractionation beyond uncertaintiesThe majority of possible HCl depletion processes at Mars yield residual HCl with lighter Cl than its source [ABSTRACT FROM AUTHOR]

Observations of water ice clouds and aerosols on Mars can provide important insights into the complexity of the water cycle. Recent observations have indicated an important link between dust activity and the water cycle, as intense dust activity can significantly raise the hygropause, and subsequently increase the escape of water after dissociation in the upper atmosphere. Here present observations from Nadir and Occultation for MArs Discovery/Trace Gas Orbiter that investigate the variation of water ice clouds in the perihelion season of Mars year 34 (April 2018–2019), their diurnal and seasonal behavior, and the vertical structure and microphysical properties of water ice and dust. These observations reveal the recurrent presence of a layer of mesospheric water ice clouds subsequent to the 2018 global dust storm. We show that this layer rose from 45 to 80 km in altitude on a time scale of days from heating in the lower atmosphere due to the storm. In addition, we demonstrate that there is a strong dawn‐dusk asymmetry in water ice abundance, related to nighttime nucleation and subsequent daytime sublimation. Water ice particle sizes are retrieved consistently and exhibit sharp vertical gradients (from 0.1 to 4.0 μm), as well as mesospheric differences between the global dust storm (<0.5 μm) and the 2019 regional dust storm (1.0 μm), which suggests differing water ice nucleation efficiencies. These results form the basis to advance our understanding of mesospheric water ice clouds on Mars, and further constrain the interactions between water ice and dust in the middle atmosphere. Key Points: Water vapor condensation rapidly responds to dust storms, increasing the altitude of mesospheric cloud formationClouds structure is observed to change between dawn and dusk, indicating nighttime nucleation of water ice on dust particlesVertical gradients in water ice particle size relate to water vapor and nuclei availability, which vary between the two dust storms of MY34 [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]

Global dust storms on Mars are rare1,2 but can affect the Martian atmosphere for several months. They can cause changes in atmospheric dynamics and inflation of the atmosphere3, primarily owing to solar heating of the dust3. In turn, changes in atmospheric dynamics can affect the distribution of atmospheric water vapour, with potential implications for the atmospheric photochemistry and climate on Mars4. 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 latitudes5,6, as well as a decrease in the water column at low latitudes7,8. 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/H2O 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 H2O 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 crystals3. The observed changes in H2O 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. High-resolution measurements of Martian atmospheric dust, water and semiheavy water, obtained by the ExoMars Trace Gas Orbiter during a global dust storm on Mars, are reported. [ABSTRACT FROM AUTHOR]

Surface transformation can affect the stability, reactivity, and toxicity of titanium dioxide (TiO2) nanoparticles (NPs) in water environments. Herein, we investigated the release kinetics of Si impurity frequently introduced during NP synthesis and the resulting effect on TiO2 NP transformation in aqueous solutions. The release of Si increased from 2 h to 19 d at three pHs with the order: pH 11.2 ≥ pH 2.4 > pH 8.2. The Si release process followed parabolic kinetics which is similar to diffusion controlled dissolution of minerals, and the release magnitude followed the order: 10 × 40 nm rutile > 50 nm anatase > 30 × 40 nm rutile. FTIR data indicated preferential dissolving of less polymerized Si species on NP surface. Surface potential and particle size of TiO2 NPs remained almost constant during the 42-day monitoring, implying the unaffected stability and transport of these NPs by the incongruent dissolution of impurities. [Copyright &y& Elsevier]

The one-dimensional steady-state expansion of a monatomic gas from a spherical source in a gravity field is studied by the direct simulation Monte Carlo method. Collisions between molecules are described by the hard sphere model, the distribution of gas molecules leaving the source surface is assumed to be Maxwellian, and no heat is directly deposited in the simulation region. The flow structure and the escape rate (number flux of molecules escaping the atmosphere) are analyzed for the source Jeans parameter λ0 (ratio of the gravitational energy to thermal energy of the molecules) and Knudsen number Kn0 (ratio of the mean free path to the source radius) ranging from 0 to 15 and from 0.0001 to ∞, respectively. In the collisionless regime, flows are analyzed for λ0=0-100 and analytical equations are obtained for asymptotic values of gas parameters that are found to be non-monotonic functions of λ0. For collisional flows, simulations predict the transition in the nature of atmospheric loss from escape on a molecule-by-molecules basis, often referred to as Jeans escape, to an organized outflow, often referred to as hydrodynamic escape. It is found that the structure of the flow and the escape rate exhibit drastic changes when λ0 varies over a narrow transition range 2-3. The lower limit of this range approximately corresponds to a critical Jeans parameter equal to 2.06, which is the upper limit for isentropic, supersonic outflow of a monatomic gas from a body in a gravity field. Subcritical, λ0≤2, flows are qualitatively similar to free outgassing in the absence of gravity, resulting in hypersonic terminal Mach numbers and escape rates that are independent of λ0 in the limit of small Knudsen numbers. Supercritical, λ0≥3, flows are controlled by thermal conduction and demonstrate qualitatively different trends. The ratio of the actual escape rate to the Jeans escape rate at the source surface is found to be a non-monotonic function of Kn0 spanning the range from ∼0.01 to ∼2. At λ0≥6, the ratio of the actual escape rate to the Jeans escape rate at the exobase is found to be ∼1.4-1.7. This is unlike the predictions of the slow hydrodynamic escape model, which is based on Parker's model for the solar wind and intended for the description of the atmospheric loss at λ0>∼10. At λ0<6, the actual escape rate can be well approximated by a modified Jeans escape rate, which accounts for non-zero gas velocity. [ABSTRACT FROM AUTHOR]

Abstract: Phosphorus-bearing materials as an additive have been popularly used in nanomaterial synthesis and the residual phosphorus within the nanoparticles (NPs) can be of an environmental concern. For instance, phosphorus within pristine commercial TiO2 NPs greatly influences the surface charge and aggregation behavior of the host TiO2 in aquatic environments; however, it is unknown whether and how fast phosphorus is released. In this study, we focus on the phosphorus release kinetics from five types of TiO2 NPs (i.e., 5, 10, and 50 nm anatase and 10 × 40, 30 × 40 nm rutile) under the influence of varying solution chemistries. The 50 nm anatase has the highest quantity of P (8.05 g/kg) and most leachable P dissolves within the first 2 h (i.e., 5.01 g/kg), which presents a potential pollutant source of P. Higher pH favors the phosphorus release (release order: pH 11.2 > pH 8.2 > pH 2.4), while variations in the environmentally relevant ionic strengths (0.01 M NaCl + 0.01 M NaHCO3 and 0.04 M NaCl + 0.01 M NaHCO3) and the presence of dissolved natural organic matter (10 mg/L) do not affect release rate greatly. X-ray Absorption Near Edge Structure results suggest that phosphate adsorbed on the pristine 50 nm anatase desorbs, and some dissolved phosphate again re-sorbs as a surface precipitate. The findings from this research may have important environmental implications such as accidental release of TiO2 NPs and other nanomaterials that are synthesized using phosphorus containing chemicals as an ingredient. [Copyright &y& Elsevier]