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The vertical opacity structure of the martian atmosphere is important for understanding the distribution of ice (water and carbon dioxide) and dust. We present a new data set of extinction opacity profiles from the NOMAD/UVIS spectrometer aboard the ExoMars Trace Gas Orbiter, covering one and a half Mars Years (MY) including the MY 34 Global Dust Storm and several regional dust storms. We discuss specific mesospheric cloud features and compare with existing literature and a Mars Global Climate Model (MGCM) run with data assimilation. Mesospheric opacity features, interpreted to be water ice, were present during the global and regional dust events and correlate with an elevated hygropause in the MGCM, providing evidence that regional dust storms can boost transport of vapor to mesospheric altitudes (with potential implications for atmospheric escape). The season of the dust storms also had an apparent impact on the resulting lifetime of the cloud features, with events earlier in the dusty season correlating with longer‐lasting mesospheric cloud layers. Mesospheric opacity features were also present during the dusty season even in the absence of regional dust storms, and interpreted to be water ice based on previous literature. The assimilated MGCM temperature structure agreed well with the UVIS opacities, but the MGCM opacity field struggled to reproduce mesospheric ice features, suggesting a need for further development of water ice parameterizations. The UVIS opacity data set offers opportunities for further research into the vertical aerosol structure of the martian atmosphere, and for validation of how this is represented in numerical models. Plain Language Summary: The martian atmosphere contains several kinds of aerosol, including dust, water ice, and carbon dioxide ice. The NOMAD/UVIS spectrometer aboard the ExoMars Trace Gas orbiter is able to measure the opacity of the atmosphere at different heights by looking through the atmosphere at the Sun, and these opacities provide information on the vertical aerosol distribution. We present a new data set of these opacities for one and a half Mars Years, a period including one Global Dust Storm and several smaller regional‐scale dust storms. By comparing with a martian climate model and previous work we discuss some noteable features in the UVIS data. We see the presence of high‐altitude water ice clouds associated with the Global Dust Storm and several regional dust storms, and find that the lifetime of these cloud layers seems to depend on the seasonal timing of the relevant dust event. These layers also correlate with an elevated higher‐altitude water vapor presence, showing that large dust storms boost the upwards transport of water vapor; this could enhance atmospheric escape of hydrogen. The model temperature structure is consistent with the UVIS results, but the model aerosol field shows a need for improvement in its representation of high‐altitude water ice. Key Points: Mesospheric water ice clouds were present in ExoMars/UVIS opacity profiles during a global and three regional dust stormsMesospheric water ice correlated with elevated hygropause, showing storms boost vertical water transport with hydrogen escape implicationsPerihelion season mesospheric water ice was also present even in the absence of global/regional dust storm activity [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 report and results of an IUPAC Task Group (TG) formed in 2004 on 'A Database of Water Transitions from Experiment and Theory' (Project No. 2004-035-1-100) are presented. Energy levels and recommended labels involving exact and approximate quantum numbers for the main isotopologues of water in the gas phase, H216O, H218O, H217O, HD16O, HD18O, HD17O, D216O, D218O, and D217O, are determined from measured transition frequencies. The transition frequencies and energy levels are validated using first-principles nuclear motion computations and the MARVEL (measured active rotational-vibrational energy levels) approach. The extensive data including lines and levels are required for analysis and synthesis of spectra, thermochemical applications, the construction of theoretical models, and the removal of spectral contamination by ubiquitous water lines. These datasets can also be used to assess where measurements are lacking for each isotopologue and to provide accurate frequencies for many yet-to-be measured transitions. The lack of high-quality frequency calibration standards in the near infrared is identified as an issue that has hindered the determination of high-accuracy energy levels at higher frequencies. The generation of spectra using the MARVEL energy levels combined with transition intensities computed using high accuracy ab initio dipole moment surfaces are discussed. A recommendation of the TG is for further work to identify a single, suitable model to represent pressure- (and temperature-) dependent line profiles more accurately than Voigt profiles. [ABSTRACT FROM AUTHOR]

We investigate water vapor saturation in the martian atmosphere in the presence or proximity of water ice clouds. We evaluate mixing ratio profiles of ambient water vapor derived from measurements by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) and the Nadir and Occultation for MArs Discovery (NOMAD) instrument in comparison with saturated vapor mixing ratio profiles derived from co-located temperature measurements by the Mars Climate Sounder (MCS). We find that during the aphelion season the average saturation state of the atmosphere is close to saturation in the presence of clouds, with supersaturation ratios reaching values of no more than two to three towards the top of the cloud layer. During the perihelion season, subseasonally averaged water vapor is close to saturation or somewhat subsaturated in the presence of clouds, with some supersaturation at southern high latitudes towards the top of the clouds. Measurements at northern mid- to high latitudes during a Global Dust Storm suggest a shift of the cloud occurrence to higher altitudes but exhibit a similar saturation structure, with supersaturations not exceeding a ratio of five. The atmosphere above cloud layers is largely subsaturated, suggesting that cloud formation is fairly instantaneous upon the temperature dropping below the frost point and high levels of supersaturation are not required to form water ice clouds. We propose a schematic model of cloud evolution in which small cloud particles are formed rapidly in slightly supersaturated regions, and then fall and grow such that ice opacity is still observed even in the subsaturated regions below. [Display omitted] • Water vapor saturation close to clouds in the martian atmosphere is investigated. • The average state of the atmosphere is close to saturation. • The atmosphere above and below cloud layers appears largely subsaturated. • High levels of supersaturation are not required to form water ice clouds. [ABSTRACT FROM AUTHOR]

Abstract: This paper is the fourth of a series of papers reporting critically evaluated rotational–vibrational line positions, transition intensities, pressure dependences, and energy levels, with associated critically reviewed assignments and uncertainties, for all the main isotopologues of water. This paper presents energy level and transition data for the following doubly and triply substituted isotopologues of water: D2 16O, D2 17O, and D2 18O. The MARVEL (Measured Active Rotational–Vibrational Energy Levels) procedure is used to determine the levels, the lines, and their self-consistent uncertainties for the spectral regions 0–14016, 0–7969, and 0–9108cm−1 for D2 16O, D2 17O, and D2 18O, respectively. For D2 16O, D2 17O, and D2 18O, 53534, 600, and 12167 lines are considered, respectively, from spectra recorded in absorption at room temperature and in emission at elevated temperatures. The number of validated energy levels is 12269, 338, and 3351 for D2 16O, D2 17O, and D2 18O, respectively. The energy levels have been checked against the ones determined, with an average accuracy of about 0.03cm−1, from variational rovibrational computations employing exact kinetic energy operators and an accurate potential energy surface. Furthermore, the rovibrational labels of the energy levels have been validated by an analysis of the computed wavefunctions using the rigid-rotor decomposition (RRD) scheme. The extensive list of MARVEL lines and levels obtained is deposited in the Supplementary Material of this paper, in a distributed information system applied to water, W@DIS, and on the official MARVEL website, where they can easily be retrieved. [Copyright &y& Elsevier]

Abstract: This is the third of a series of articles reporting critically evaluated rotational–vibrational line positions, transition intensities, and energy levels, with associated critically reviewed labels and uncertainties, for all the main isotopologues of water. This paper presents experimental line positions, experimental-quality energy levels, and validated labels for rotational–vibrational transitions of the most abundant isotopologue of water, H2 16O. The latest version of the MARVEL (Measured Active Rotational–Vibrational Energy Levels) line-inversion procedure is used to determine the rovibrational energy levels of the electronic ground state of H2 16O from experimentally measured lines, together with their self-consistent uncertainties, for the spectral region up to the first dissociation limit. The spectroscopic network of H2 16O containstwo components, an ortho (o) and a para (p) one. For o-H2 16O and p-H2 16O, experimentally measured, assigned, and labeled transitions were analyzed from more than 100 sources. The measured lines come from one-photon spectra recorded at room temperature in absorption, from hot samples with temperatures up to 3000K recorded in emission, and from multiresonance excitation spectra which sample levels up to dissociation. The total number of transitions considered is 184667 of which 182156 are validated: 68027 between para states and 114129 ortho ones. These transitions give rise to 18486 validated energy levels, of which 10446 and 8040 belong to o-H2 16O and p-H2 16O, respectively. The energy levels, including their labeling with approximate normal-mode and rigid-rotor quantum numbers, have been checked against ones determined from accurate variational nuclear motion computations employing exact kinetic energy operators as well as against previous compilations of energy levels. The extensive list of MARVEL lines and levels obtained are deposited in the supplementary data of this paper, as well as in a distributed information system applied to water, W@DIS, where they can easily be retrieved. [Copyright &y& Elsevier]

Abstract: High-resolution water vapor absorption spectra have been measured at room temperature in the 8800–11,600cm−1 spectral region. They were obtained using the mobile BRUKER IFS 120M Fourier transform spectrometer (FTS) from ULB-SCQP coupled to the 50m base long multiple reflection White type cell in GSMA laboratory. The absorption path was 600m and different H2O/HDO/D2O mixtures were used. Measurements of line positions, intensities and self-broadening coefficients were performed for the HD16O isotopologue. 6464 rovibrational assignment of the observed lines was made on the basis of global variational predictions and allowed the identification of new energy levels. 3ν 3, 2ν 1+ν 3, 3ν 1+ν 2, ν 1+2ν 3 and 2ν 2+2ν 3 are the five strongest bands. The present paper provides a complementary data set on water vapor for atmospheric and astrophysical applications. [Copyright &y& Elsevier]

Abstract: This is the second of a series of articles reporting critically evaluated rotational–vibrational line positions, transition intensities, pressure dependences, and energy levels, with associated critically reviewed assignments and uncertainties, for all the main isotopologues of water. This article presents energy levels and line positions of the following singly deuterated isotopologues of water: HD16O, HD17O, and HD18O. The MARVEL (measured active rotational–vibrational energy levels) procedure is used to determine the levels, the lines, and their self-consistent uncertainties for the spectral regions 0–22708, 0–1674, and 0–12105cm−1 for HD16O, HD17O, and HD18O, respectively. For HD16O, 54740 transitions were analyzed from 76 sources, the lines come from spectra recorded both at room temperature and from hot samples. These lines correspond to 36690 distinct assignments and 8818 energy levels. For HD17O, only 485 transitions could be analyzed from three sources; the lines correspond to 162 MARVEL energy levels. For HD18O, 8729 transitions were analyzed from 11 sources and these lines correspond to 1864 energy levels. The energy levels are checked against ones determined from accurate variational nuclear motion computations employing exact kinetic energy operators. This comparison shows that the measured transitions account for about 86% of the anticipated absorbance of HD16O at 296K and that the transitions predicted by the MARVEL energy levels account for essentially all the remaining absorbance. The extensive list of MARVEL lines and levels obtained are given in the Supplementary Material of this article, as well as in a distributed information system applied to water, W@DIS, where they can easily be retrieved. In addition, the transition and energy level information for H2 17O and H2 18O, given in the first paper of this series [Tennyson, et al. J Quant Spectr Rad Transfer 2009;110:573–96], has been updated. [Copyright &y& Elsevier]

Abstract: This is the first part of a series of articles reporting critically evaluated rotational–vibrational line positions, transition intensities, pressure dependence and energy levels, with associated critically reviewed assignments and uncertainties, for all the main isotopologues of water. The present article contains energy levels and data for line positions of the singly substituted isotopologues H2 17Oand H2 18O. The procedure and code MARVEL, standing for measured active rotational–vibrational energy levels, is used extensively in all stages of determining the validated levels and lines and their self-consistent uncertainties. The spectral regions covered for both isotopologues H2 17O and H2 18O are . The energy levels are checked against ones determined from accurate variational calculations. The number of critically evaluated and recommended levels and lines are, respectively, 2687 and 8614 for H2 17O, and 4839 and 29364 for H2 18O. The extensive lists of MARVEL lines and levels obtained are deposited in the Supplementary Material, as well as in a distributed information system applied to water, W@DIS, where they can easily be retrieved. A distinguishing feature of the present evaluation of water spectroscopic data is the systematic use of all available experimental data and validation by first-principles theoretical calculations. [Copyright &y& Elsevier]

Abstract: New high-resolution water vapor absorption spectra were obtained at room temperature in the 4200–6600cm−1 spectral region by combining Fourier transform spectrometers (FTS) with single and multiple reflection cells. With absorption paths from 0.3 to 1800 m in pure and air diluted water vapor, accurate measurements of about 10400 lines in an intensity range from 10−29 to 10−19 cm/molecule have been performed. Positions, intensities, self- and air-broadening coefficients and air-induced shifts were determined for the H2 16O, H2 17O, H2 18O and HDO isotopologues. The rovibrational assignment of the observed lines was performed with the use of global variational predictions and allowed the identification of several new energy levels. One major contribution of this work consists of the identification of 3280 new weak lines. A very close agreement between the new measured parameters and those listed in the database is reported as well as between the observations and the most recent variational calculations for the positions and the intensities. The present parameters provide an extended and homogeneous data set for water vapor, which is shown to significantly improve the databases for atmospheric applications, especially in the transmission windows on both sides of the band centered at 5400cm−1. [Copyright &y& Elsevier]

The absorption of solar light by atmospheric water vapor in the visible spectral region is analyzed by means of ground-based absorption Fourier transform spectroscopy, performed at high resolution in Brussels during summer 2001. Several microwindows between 14,000 and 18,000 cm−1, in which water vapor lines are well isolated from solar lines and other atmospheric trace gases absorptions, are examined. They are demonstrated to be adequate for the retrieval of the total water vapor column. Based on the retrievals, a detailed analysis of the water vapor line parameters published in the HITRAN database and recently reinvestigated by different groups is performed. The analysis focuses on the one hand on the comparison of the retrieved water vapor columns with in situ measurements, performed at the same time as the spectroscopic measurements and at the same location, and on the other hand on the quality of the spectral fits. It is shown that the discrepancies between the line lists affect significantly the results. In particular it is shown that the weaker lines, not measured in earlier laboratory experiments, do contribute at large zenith angles and need to be taken into account in order to better simulate the atmospheric spectra. The importance of the pressure broadening parameters is also highlighted. [Copyright &y& Elsevier]

Considering the unique role that water in its vapor phase plays in atmospheric physical and chemical processes, there is a need for accurate spectroscopic parameters for this molecule. Long-pathlength Fourier transform spectra of water vapor with synthetic air as the perturbing gas were recorded and analyzed in the 26,000–13,000 cm−1 spectral region. New measurements of air-broadening and air-shifting parameters with associated uncertainties are presented for about 5000 lines. These data complement our existing database, providing a homogeneous and extensive dataset extending from 26,000 to 9250 cm−1. Comparisons with the two most frequently used HITRAN and ESA databases as well as with other literature data available are made. Agreements and discrepancies are underlined and briefly discussed. [Copyright &y& Elsevier]

Line parameters of water vapor have been obtained in the 13 000–9250 cm−1 spectral region. The measurements were performed with a high resolution Fourier transform spectrometer coupled to long-path multiple reflection cells. Emphasis was put on the determination of accurate parameters for the weak lines, most of which have not been previously reported in the literature. A total of 7061 lines have been studied. Their positions and intensities have been determined, and for many of analyzed lines, self- and air-broadening coefficients, as well as pressure-induced shifts were obtained. A preliminary analysis of the dependence of the broadenings and shifts, with vibrational and rotational quantum numbers is given. The discussion is focused on the comparison between our measured parameters and those listed in the HITRAN database. A very good agreement is reported for the positions and intensities. It is suggested that the construction of a comprehensive and complete dataset for water vapor in this spectral region requires the merging of independent measurements, and of calculated values of broadenings and shifts for weak and blended lines. [Copyright &y& Elsevier]

The radiative properties of water vapor play an important role in the physical and chemical processes occurring in the atmosphere. Accurate knowledge of the line parameters for this species is therefore needed. This work presents new measurements of water vapor line parameters in the 26 000–13 000 cm−1 spectral region. The measurements were obtained by combining a high-resolution Fourier transform spectrometer with a long-path absorption cell, thus allowing the observation of very weak, previously unobserved, lines. A total of more than 9000 lines have been identified and their position, integrated cross section and self-broadening parameter have been determined. The dependence of the line parameters on nitrogen buffer gas pressure (0–800 hPa) has also been studied. The complete line list presented here is primarily compared to the HITRAN spectroscopic database, most frequently used in atmospheric calculations. [Copyright &y& Elsevier]