Diurnal variation of the potassium layer in the upper atmosphere

Measurements of the diurnal cycle of potassium (K) atoms between 80 and 110km have been made during October (for the years 2004–2011) using a Doppler lidar at Kühlungsborn, Germany (54.1°N,11.7°E). A pronounced diurnal variation is observed in the K number density, which is explored by using a detailed description of the neutral and ionized chemistry of K in a three-dimensional chemistry climate model. The model captures both the amplitude and phase of the diurnal and semidiurnal variability of the layer, although the peak diurnal amplitude around 90 kmis overestimated. Themodel shows that the total potassium density (≈K+K++KHCO3) exhibits little diurnal variation at each altitude, and the diurnal variations are largely driven by photochemical conversion between these reservoir species. In contrast, tidally driven vertical transport has a small effect at this midlatitude location, and diurnal fluctuations in temperature are of little significance because they are small and the chemistry of K is relatively temperature independent

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

Modelling the impact of noctilucent cloud formation on atomic oxygen and other minor constituents of the summer mesosphere

International audienceThe formation, evolution and eventual sublimation of noctilucent clouds (NLC) may have a significant effect on the odd oxygen and hydrogen chemistry of the high latitude summer mesosphere. Three mechanisms are considered here: the direct uptake of atomic oxygen on the surface of the ice particles; the redistribution of water vapour, which changes the photochemical source of odd hydrogen species; and the direct photolysis of the ice particles themselves to produce odd hydrogen species in the gas phase. A 1-D photochemical model is employed to investigate the potential importance of these mechanisms. This shows, using the recently measured uptake coefficients of O on ice, that the heterogeneous removal of O on the surface of the cloud particles is too slow by at least a factor of 5x103 to compete with gas-phase O chemistry. The second and third mechanisms involve the solar Lyman-? photolysis of H2O in the gas and solid phase, respectively. During twilight, Lyman-? radiation is severely attenuated and these mechanisms are insignificant. In contrast, when the upper mesosphere is fully illuminated there is a dramatic impact on the O profile, with depletion of O at the base of the cloud layer of close to an order of magnitude. A correspondingly large depletion in O3 is also predicted, while H, OH, HO2 and H2O2 are found to be enhanced by factors of 3-5. In fact, rocket-borne mass spectrometer measurements during summer have revealed local H2O2 enhancements in the region of the clouds. Rocket-borne measurements of atomic O and O3 profiles in the presence of mesospheric clouds in the daytime are highly desirable to test the predictions of this model and our understanding of the genesis of mesospheric clouds

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

On the size and velocity distribution of cosmic dust particles entering the atmosphere

The size and velocity distribution of cosmic dust particles entering the Earth's atmosphere is uncertain. Here we show that the relative concentrations of metal atoms in the upper mesosphere, and the surface accretion rate of cosmic spherules, provide sensitive probes of this distribution. Three cosmic dust models are selected as case studies: two are astronomical models, the first constrained by infrared observations of the Zodiacal Dust Cloud and the second by radar observations of meteor head echoes; the third model is based on measurements made with a spaceborne dust detector. For each model, a Monte Carlo sampling method combined with a chemical ablation model is used to predict the ablation rates of Na, K, Fe, Mg, and Ca above 60 km and cosmic spherule production rate. It appears that a significant fraction of the cosmic dust consists of small (<5 µg) and slow (<15 km s−1) particles

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

Chemical modeling for pH prediction of acidified musts with gypsum and tartaric acid in warm regions

Winemaking of musts acidified with up to 3 g/L of gypsum (CaSO4 2H2O) and tartaric acid, both individually and in combination, as well as a chemical modeling have been carried out to study the behaviour of these compounds as acidifiers. Prior to fermentation gypsum and tartaric acid reduce the pH by 0.12 and 0.17 pH units/g/L, respectively, but while gypsum does not increase the total acidity and reduces buffering power, tartaric acid shows the opposite behaviour. When these compounds were used in combination, the doses of tartaric acid necessary to reach a suitable pH were reduced. Calcium concentrations increase considerably in gypsum-acidified must, although they fell markedly after fermentation over time. Sulfate concentrations also increased, although with doses of 2 g/L they were lower than the maximum permitted level (2.5 g/L). Chemical modeling gave good results and the errors in pH predictions were less than 5% in almost all case

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