Explore the vast range of titles available.

Spectroscopic observations of exoplanets are now possible by transit methods and direct emission. Spectroscopic requirements for exoplanets are reviewed based on existing measurements and model predictions for hot Jupiters and super-Earths. Molecular opacities needed to simulate astronomical observations can be obtained from laboratory measurements, ab initio calculations or a combination of the two approaches. This discussion article focuses mainly on laboratory measurements of hot molecules as needed for exoplanet spectroscopy.

The report of an IUPAC Task Group, formed in 2011 on “Intensities and line shapes in high-resolution spectra of water isotopologues from experiment and theory” (Project No. 2011-022-2-100), on line profiles of isolated high-resolution rotational-vibrational transitions perturbed by neutral gas-phase molecules is presented. The well-documented inadequacies of the Voigt profile (VP), used almost universally by databases and radiative-transfer codes, to represent pressure effects and Doppler broadening in isolated vibrational-rotational and pure rotational transitions of the water molecule have resulted in the development of a variety of alternative line-profile models. These models capture more of the physics of the influence of pressure on line shapes but, in general, at the price of greater complexity. The Task Group recommends that the partially Correlated quadratic-Speed-Dependent Hard-Collision profile (pCqSD-HCP) should be adopted as the appropriate model for high-resolution spectroscopy. For simplicity this should be called the Hartmann–Tran profile (HTP). The HTP is sophisticated enough to capture the various collisional contributions to the isolated line shape, can be computed in a straightforward and rapid manner, and reduces to simpler profiles, including the Voigt profile, under certain simplifying assumptions.

Massive Australian wildfires lofted smoke directly into the stratosphere in the austral summer of 2019/20. The smoke led to increases in optical extinction throughout the midlatitudes of the southern hemisphere that rivalled substantial volcanic perturbations. Previous studies have assumed that the smoke became coated with sulfuric acid and water and would deplete the ozone layer through heterogeneous chemistry on those surfaces, as is routinely observed following volcanic enhancements of the stratospheric sulfate layer. Here, observations of extinction and reactive nitrogen species from multiple independent satellites that sampled the smoke region are compared to one another and to model calculations. The data display a strong decrease in reactive nitrogen concentrations with increased aerosol extinction in the stratosphere, which is a known fingerprint for key heterogeneous chemistry on sulfate/H₂O particles (specifically the hydrolysis of N₂O₅ to form HNO₃). This chemical shift affects not only reactive nitrogen but also chlorine and reactive hydrogen species and is expected to cause midlatitude ozone layer depletion. Comparison of the model ozone to observations suggests that N₂O₅ hydrolysis contributed to reduced ozone, but additional chemical and/or dynamical processes are also important. These findings suggest that if wildfire smoke injection into the stratosphere increases sufficiently in frequency and magnitude as the world warms due to climate change, ozone recovery under the Montreal Protocol could be impeded, at least sporadically. Modeled austral midlatitude total ozone loss was about 1% in March 2020, which is significant compared to expected ozone recovery of about 1% per decade.

The Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) uses limb geometry to measure transmittance spectra of Earth's atmosphere by solar occultation. Line-of-sight wind speeds can be derived via Doppler shifts of molecular lines in infrared spectra. The wind look direction angles relative to geodetic north are derived from geometry. We validate the new ACE version 5.3 (v.5.3) line-of-sight winds with MIGHTI and meteor radar vector wind observations and find a -15 m s−1 (+15 m s−1) sunrise (sunset) shift above 80 km. We also compare line-of-sight winds from ACE-FTS v.5.2 and v.5.3 with vector winds from the MERRA-2, HWM14, and WACCM-X models. A -15 to -20 m s−1 (+15 to +20 m s−1) sunrise (sunset) bias persists in v.5.3 winds above 80 km but decreases to less than -5 m s−1 (+5 m s−1) below 50 km. The v.5.3 wind speed profiles have improved relative to v.5.2 at all altitudes. Over 20 years of ACE wind speeds can be used to test atmospheric models.

Transport of air from the troposphere to the stratosphere occurs primarily in the tropics, associated with the ascending branch of the Brewer-Dobson circulation. Here, we identify the transport of air masses from the surface, through the Asian monsoon, and deep into the stratosphere, using satellite observations of hydrogen cyanide (HCN), a tropospheric pollutant produced in biomass burning. A key factor in this identification is that HCN has a strong sink from contact with the ocean; much of the air in the tropical upper troposphere is relatively depleted in HCN, and hence, broad tropical upwelling cannot be the main source for the stratosphere. The monsoon circulation provides an effective pathway for pollution from Asia, India, and Indonesia to enter the global stratosphere.

Evaluating the representation of processes controlling tropical and subtropical tropospheric relative humidity (RH) in atmospheric general circulation models (GCMs) is crucial to assess the credibility of predicted climate changes. GCMs have long exhibited a moist bias in the tropical and subtropical mid and upper troposphere, which could be due to the mis‐representation of cloud processes or of the large‐scale circulation, or to excessive diffusion during water vapor transport. The goal of this study is to use observations of the water vapor isotopic ratio to understand the cause of this bias. We compare the three‐dimensional distribution of the water vapor isotopic ratio measured from space and ground to that simulated by several versions of the isotopic GCM LMDZ. We show that the combined evaluation of RH and of the water vapor isotopic composition makes it possible to discriminate the most likely cause of RH biases. Models characterized either by an excessive vertical diffusion, an excessive convective detrainment or an underestimated in situ cloud condensation will all produce a moist bias in the free troposphere. However, only an excessive vertical diffusion can lead to a reversed seasonality of the free tropospheric isotopic composition in the subtropics compared to observations. Comparing seven isotopic GCMs suggests that the moist bias found in many GCMs in the mid and upper troposphere most frequently results from an excessive diffusion during vertical water vapor transport. This study demonstrates the added value of water vapor isotopic measurements for interpreting shortcomings in the simulation of RH by climate models. Key Points Water vapor isotopes= observational diagnostics to evaluate RH in GCMs Excessive vertical diffusion= widespread cause of moist bias in GCMs Parameterized processes =larger uncertainty for RH than large‐scale circulation

Line-of-sight wind profiles are derived from Doppler shifts in infrared solar occultation measurements from the Atmospheric Chemistry Experiment Fourier transform spectrometers (ACE-FTS), the primary instrument on SCISAT, a satellite-based mission for monitoring the Earth’s atmosphere. Comparisons suggest a possible eastward bias from 20 m/s to 30 m/s in ACE-FTS results above 80 km relative to some datasets but no persistent bias relative to other datasets. For instruments operating in a limb geometry, looking through a wide range of altitudes, smearing of the Doppler effect along the line of sight can impact the measured signal, particularly for saturated absorption lines. Implications of Doppler effect smearing are investigated for forward model calculations and volume mixing ratio retrievals. Effects are generally small enough to be safely ignored, except for molecules having a large overhang in their volume mixing ratio profile, such as carbon monoxide.

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, H O, H O, H O, HD O, HD O, HD O, D O, D O, and D O, 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.

High‐quality satellite observations of water and deuterated water in the upper troposphere and lower stratosphere (UTLS) from the Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE‐FTS) are used to map global climatological behavior. Spatial and temporal variability in these data suggest that convection plays a significant role in setting water vapor isotopic composition in these regions. In many instances, enhancements in HDO/H2O (i.e., δD) are closely tied to patterns of climatological deep convection and uncorrelated with water vapor, although convection appears to have different isotopic effects in different locations. The ACE‐FTS data reveal seasonal variations in the tropics and allow mapping of climatological regional structure. These data reveal strong regional isotopic enhancement associated with the North American summer monsoon but not the Asian monsoon or the western Pacific warm pool. We suggest that the isotopic effects of deep convection near the tropopause are moderated by the ambient relative humidity, which controls the amount of convective ice that evaporates. Local convective signals can in turn affect global behavior: the North America monsoon influence introduces a Northern Hemisphere–Southern Hemisphere asymmetry in water isotopic composition in the lower stratosphere that extends into the tropics and influences the apparent seasonal cycle in averaged tropical UTLS data. Seasonal variation in tropical lower stratospheric water isotopic composition extends up to ∼20 km in ACE retrievals, but in contrast to previous reports, there is no clear evidence of propagation beyond the lowermost stratosphere. The reliability of these observations is supported by the broad consistency of ACE‐FTS averaged tropical profiles with previous remote and in situ δD measurements. Key Points Novel global climatology of HDO from satellite measurements HDO isotopic ratios exhibit regional and seasonal variability Strong HDO enrichment linked to NA summer monsoon

It is known from ground-based measurements made during the 1982–1983 and 1997–1998 El Niño events that atmospheric hydrogen cyanide (HCN) tends to be higher during such years than at other times. The Microwave Limb Sounder (MLS) on the Aura satellite has been measuring HCN mixing ratios since launch in 2004; the measurements are ongoing at the time of writing. The winter of 2015–2016 saw the largest El Niño event since 1997–1998. We present MLS measurements of HCN in the lower stratosphere for the Aura mission to date, comparing the 2015–2016 El Niño period to the rest of the mission. HCN in 2015–2016 is higher than at any other time during the mission, but ground-based measurements suggest that it may have been even more elevated in 1997–1998. As the MLS HCN data are essentially unvalidated, we show them alongside data from the MIPAS and ACE-FTS instruments; the three instruments agree reasonably well in the tropical lower stratosphere. Global HCN emissions calculated from the Global Fire Emissions Database (GFED v4.1) database are much greater during large El Niño events and are greater in 1997–1998 than in 2015–2016, thereby showing good qualitative agreement with the measurements. Correlation between El Niño–Southern Oscillation (ENSO) indices, measured HCN, and GFED HCN emissions is less clear if the 2015–2016 event is excluded. In particular, the 2009–2010 winter had fairly strong El Niño conditions and fairly large GFED HCN emissions, but very little effect is observed in the MLS HCN.