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

The Meteoric Ni Layer in the Upper Atmosphere

The first global atmospheric model of Ni (WACCM-Ni) has been developed to understand recent observations of the mesospheric Ni layer by ground-based resonance lidars. The three components of the model are: the Whole Atmospheric Community Climate Model (WACCM6); a meteoric input function derived by coupling an astronomical model of dust sources in the solar system with a chemical meteoric ablation model; and a comprehensive set of neutral, ion-molecule, and photochemical reactions pertinent to the chemistry of Ni in the upper atmosphere. In order to achieve closure on the chemistry, the reaction kinetics of three important reactions were first studied using a fast flow tube with pulsed laser ablation of a Ni target, yielding k(NiO + O) = (4.6 ± 1.4) × 10−11, k(NiO + CO) = (3.0 ± 0.5) × 10−11, and k(NiO2 + O) = (2.5 ± 1.2) × 10−11 cm3 molecule−1 s−1 at 294 K. The photodissociation rate of NiOH was computed to be J(NiOH) = 0.02 s−1. WACCM-Ni simulates satisfactorily the observed neutral Ni layer peak height and width, and Ni+ measurements from rocket-borne mass spectrometry. The Ni layer is predicted to have a similar seasonal and latitudinal variation as the Fe layer, and its unusually broad bottom-side compared with Fe is caused by the relatively fast NiO + CO reaction. The quantum yield for photon emission from the Ni + O3 reaction, observed in the nightglow, is estimated to be between 6% and 40%. ©2020. The Authors

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

Three-dimensional model study of the Arctic ozone loss in 2002/2003 and comparison with 1999/2000 and 2003/2004

We have used the SLIMCAT 3-D off-line chemical transport model (CTM) to quantify the Arctic chemical ozone loss in the year 2002/2003 and compare it with similar calculations for the winters 1999/2000 and 2003/2004. Recent changes to the CTM have improved the model's ability to reproduce polar chemical and dynamical processes. The updated CTM uses σ-θ as a vertical coordinate which allows it to extend down to the surface. The CTM has a detailed stratospheric chemistry scheme and now includes a simple NAT-based denitrification scheme in the stratosphere. In the model runs presented here the model was forced by ECMWF ERA40 and operational analyses. The model used 24 levels extending from the surface to ~55km and a horizontal resolution of either 7.5° x 7.5° or 2.8° x 2.8°. Two different radiation schemes, MIDRAD and the CCM scheme, were used to diagnose the vertical motion in the stratosphere. Based on tracer observations from balloons and aircraft, the more sophisticated CCM scheme gives a better representation of the vertical transport in this model which includes the troposphere. The higher resolution model generally produces larger chemical O3 depletion, which agrees better with observations. The CTM results show that very early chemical ozone loss occurred in December 2002 due to extremely low temperatures and early chlorine activation in the lower stratosphere. Thus, chemical loss in this winter started earlier than in the other two winters studied here. In 2002/2003 the local polar ozone loss in the lower stratosphere was ~40% before the stratospheric final warming. Larger ozone loss occurred in the cold year 1999/2000 which had a persistently cold and stable vortex during most of the winter. For this winter the current model, at a resolution of 2.8° x 2.8°, can reproduce the observed loss of over 70% locally. In the warm and more disturbed winter 2003/2004 the chemical O3 loss was generally much smaller, except above 620K where large losses occurred due to a period of very low minimum temperatures at these altitudes

Influence of the Arctic Oscillation on the Vertical Distribution of Wintertime Ozone in the Stratosphere and Upper Troposphere over Northern Hemisphere

The influence of the Arctic Oscillation (AO) on the vertical distribution of stratospheric ozone in the Northern Hemisphere in winter is analyzed using observations and an offline chemical transport model. Positive ozone anomalies are found at low latitudes (0–30°N) and there are three negative anomaly centers in the northern mid- and high latitudes during positive AO phases. The negative anomalies are located in the Arctic middle stratosphere (~30 hPa, 70–90°N), Arctic upper troposphere/lower stratosphere (UTLS, 150–300 hPa, 70–90°N), and mid-latitude UTLS (70–300 hPa, 30–60°N). Further analysis shows that anomalous dynamical transport related to AO variability primarily controls these ozone changes. During positive AO events, positive ozone anomalies between 0–30°N at 50–150 hPa are related to the weakened meridional transport of the Brewer–Dobson circulation (BDC) and enhanced eddy transport. The negative ozone anomalies in the Arctic middle stratosphere are also caused by the weakened BDC, while the negative ozone anomalies in the Arctic UTLS are caused by the increased tropopause height, weakened BDC vertical transport, weaker exchange between the mid-latitudes and the Arctic, and enhanced ozone depletion via heterogeneous chemistry. The negative ozone anomalies in the mid-latitude UTLS are due mainly to enhanced eddy transport from the mid-latitudes to the equatorward of 30°N, while the transport of ozone-poor air from the Arctic to the mid-latitudes makes a minor contribution. Interpreting AO-related variability of stratospheric ozone, especially in the UTLS, would be helpful for the prediction of tropospheric ozone variability caused by AO