Photoelectric emission from the alkali metal doped vacuum-ice interface

The photoelectron photoemission spectra and thresholds for low coverages of Li and K adsorbed on water-ice have been measured, compared with photoionization spectra of the gas-phase atoms, and modeled by quantum chemical calculations. For both alkali metals the threshold for photoemission is dramatically decreased and the cross section increased on adsorption to the water-ice surface. Quantum chemical calculations suggest that the initial state is formed by the metal atoms adsorbed into the water-ice surface, forming a state with a delocalized electron distribution. This state is metastable and decays on the hundreds of seconds time scale at 92 K. The decay is markedly faster for Li than for K, probably due to diffusion into the ice film

Photochemistry on the Bottom Side of the Mesospheric Na Layer

Lidar observations of the mesospheric Na layer have revealed considerable diurnal variations, particularly on the bottom side of the layer, where more than an order-of-magnitude increase in Na density has been observed below 80 km after sunrise. In this paper, multi-year Na lidar observations are utilized over a full diurnal cycle at Utah State University (USU) (41.8o N, 111.8o W) and a global atmospheric model of Na with 0.5 km vertical resolution in the mesosphere and lower thermosphere (WACCM-Na) to explore the dramatic changes of Na density on the bottom side of the layer. Photolysis of the principal reservoir NaHCO3 is shown to be primarily responsible for the increase in Na after sunrise, amplified by the increased rate of reaction of NaHCO3 with atomic H, which is mainly produced from the photolysis of H2O and the reaction of OH with O3. This finding is further supported by Na lidar observation at USU during the solar eclipse (\u3e96 % totality) event on 21 August 2017, when a decrease and recovery of the Na density on the bottom side of the layer were observed. Lastly, the model simulation shows that the Fe density below around 80 km increases more strongly and earlier than observed Na changes during sunrise because of the considerably faster photolysis rate of its major reservoir of FeOH

A Global Model of Meteoric Sodium

A global model of sodium in the mesosphere and lower thermosphere has been developed within the framework of the National Center for Atmospheric Research's Whole Atmosphere Community Climate Model (WACCM). The standard fully interactive WACCM chemistry module has been augmented with a chemistry scheme that includes nine neutral and ionized sodium species. Meteoric ablation provides the source of sodium in the model and is represented as a combination of a meteoroid input function (MIF) and a parameterized ablation model. The MIF provides the seasonally and latitudinally varying meteoric flux which is modeled taking into consideration the astronomical origins of sporadic meteors and considers variations in particle entry angle, velocity, mass, and the differential ablation of the chemical constituents. WACCM simulations show large variations in the sodium constituents over time scales from days to months. Seasonality of sodium constituents is strongly affected by variations in the MIF and transport via the mean meridional wind. In particular, the summer to winter hemisphere flow leads to the highest sodium species concentrations and loss rates occurring over the winter pole. In the Northern Hemisphere, this winter maximum can be dramatically affected by stratospheric sudden warmings. Simulations of the January 2009 major warming event show that it caused a short-term decrease in the sodium column over the polar cap that was followed by a factor of 3 increase in the following weeks. Overall, the modeled distribution of atomic sodium in WACCM agrees well with both ground-based and satellite observations. Given the strong sensitivity of the sodium layer to dynamical motions, reproducing its variability provides a stringent test of global models and should help to constrain key atmospheric variables in this poorly sampled region of the atmosphere

A new model of meteoric calcium in the mesosphere and lower thermosphere

Meteoric ablation produces layers of metal atoms in the mesosphere and lower thermosphere (MLT). It has been known for more than 30 years that the Ca atom layer is depleted by over 2 orders of magnitude compared with Na, despite these elements having nearly the same elemental abundance in chondritic meteorites. In contrast, the Ca+ ion abundance is depleted by less than a factor of 10. To explain these observations, a large database of neutral and ion–molecule reaction kinetics of Ca species, measured over the past decade, was incorporated into the Whole Atmosphere Community Climate Model (WACCM). A new meteoric input function for Ca and Na, derived using a chemical ablation model that has been tested experimentally with a Meteoric Ablation Simulator, shows that Ca ablates almost 1 order of magnitude less efficiently than Na. WACCM-Ca simulates the seasonal Ca layer satisfactorily when compared with lidar observations, but tends to overestimate Ca+ measurements made by rocket mass spectrometry and lidar. A key finding is that CaOH and CaCO3 are very stable reservoir species because they are involved in essentially closed reaction cycles with O2 and O. This has been demonstrated experimentally for CaOH, and in this study for CaCO3 using electronic structure and statistical rate theory. Most of the neutral Ca is therefore locked in these reservoirs, enabling rapid loss through polymerization into meteoric smoke particles, and this explains the extreme depletion of Ca

Measurements of the vertical fluxes of atomic Fe and Na at the mesopause: implications for the velocity of cosmic dust entering the atmosphere

The downward fluxes of Fe and Na, measured near the mesopause with the University of Colorado lidars near Boulder, and a chemical ablation model developed at the University of Leeds, are used to constrain the velocity/mass distribution of the meteoroids entering the atmosphere and to derive an improved estimate for the global influx of cosmic dust. We find that the particles responsible for injecting a large fraction of the ablated material into the Earth's upper atmosphere enter at relatively slow speeds and originate primarily from the Jupiter Family of Comets. The global mean Na influx is 17,200 ± 2800 atoms/cm2/s, which equals 298 ± 47 kg/d for the global input of Na vapor and 150 ± 38 t/d for the global influx of cosmic dust. The global mean Fe influx is 102,000 ± 18,000 atoms/cm2/s, which equals 4.29 ± 0.75 t/d for the global input of Fe vapor

Momentum Flux Spectra of a Mountain Wave Event Over New Zealand

During the Deep Propagating Gravity Wave Experiment (DEEPWAVE) 13 July 2014 research flight over the South Island of New Zealand, a multiscale spectrum of mountain waves (MWs) was observed. High-resolution measurements of sodium densities were available from ~70 to 100 km for the duration of this flight. A comprehensive technique is presented for obtaining temperature perturbations, T′, from sodium mixing ratios over a range of altitudes, and these T′ were used to calculate the momentum flux (MF) spectra with respect to horizontal wavelengths, λH, for each flight segment. Spectral analysis revealed MWs with spectral power centered at λH of ~80, 120, and 220 km. The temperature amplitudes of these MWs varied between the four cross-mountain flight legs occurring between 6:10UT and 9:10UT. The average spectral T′ amplitudes near 80 km in altitude ranged from 7–13 K for the 220 km λH MW and 4–8 K for the smaller λH MWs. These amplitudes decayed significantly up to 90 km, where a critical level for MWs was present. The average MF per unit mass near 80 km in altitude ranged from ~13 to 60 m2/s2 across the varying spectra over the duration of the research flight and decayed to ~0 by 88 km in altitude. These MFs are large compared to zonal means and highlight the importance of MWs in the momentum budget of the mesosphere and lower thermosphere at times when they reach these altitudes

Glyoxal observations in the global marine boundary layer

Glyoxal is an important intermediate species formed by the oxidation of common biogenic and anthropogenic volatile organic compounds such as isoprene, toluene and acetylene. Although glyoxal has been shown to play an important role in urban and forested environments, its role in the open ocean environment is still not well understood, with only a few observations showing evidence for its presence in the open ocean marine boundary layer (MBL). In this study, we report observations of glyoxal from ten field campaigns in different parts of the world's oceans. These observations together represent the largest database of glyoxal in the MBL. The measurements are made with similar instruments that have been used in the past, although the open ocean values reported here, average of about 25 pptv with an upper limit of 40 pptv, are much lower than previously reported observations that were consistently higher than 40 pptv and had an upper limit of 140 pptv, highlighting the uncertainties in the Differential Optical Absorption Spectroscopy (DOAS) method for the retrieval of glyoxal. Despite retrieval uncertainties, the results reported in this work support previous suggestions that the currently known sources of glyoxal are insufficient to explain the average MBL concentrations. This suggests that there is an additional missing source, more than a magnitude larger than currently known sources, which is necessary to account for the observed atmospheric levels of glyoxal. Therefore it could play a more important role in the MBL than previously considered

Structure, variability, and origin of the low-latitude nightglow continuum between 300 and 1,800 nm

The Earth's nighttime radiation in the range from the near-UV to the near-IR mainly originates between 75 and 105 km and consists of lines of different species, which are important indicators of the chemistry and dynamics at these altitudes. Based on astronomical spectra, we have characterised the structure and variability of a pseudo-continuum of a high number of faint lines and discovered a new emission process in the near-IR. By means of simulations, we identified HO2 as the likely emitter