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- ItemRetrievals of chlorine chemistry kinetic parameters from Antarctic ClO microwave radiometer measurements(München : European Geopyhsical Union, 2011) Kremser, S.; Schofield, R.; Bodeker, G.E.; Connor, B.J.; Rex, M.; Barret, J.; Mooney, T.; Salawitch, R.J.; Canty, T.; Frieler, K.; Chipperfield, M.P.; Langematz, U.; Feng, W.Key kinetic parameters governing the partitioning of chlorine species in the Antarctic polar stratosphere were retrieved from 28 days of chlorine monoxide (ClO) microwave radiometer measurements made during the late winter/early spring of 2005 at Scott Base (77.85° S, 166.75° E). During day-time the loss of the ClO dimer chlorine peroxide (ClOOCl) occurs mainly by photolysis. Some time after sunrise, a photochemical equilibrium is established and the ClO/ClOOCl partitioning is determined by the ratio of the photolysis frequency, J, and the dimer formation rate, kf. The values of J and kf from laboratory studies remain uncertain to a considerable extent, and as a complement to these ongoing studies, the goal of this work is to provide a constraint on that uncertainty based on observations of ClO profiles in the Antarctic. First an optimal estimation technique was used to derive J/kf ratios for a range of Keq values. The optimal estimation forward model was a photochemical box model that takes J, kf, and Keq as inputs, together with a priori profiles of activated chlorine (ClOx = ClO+2×ClOOCl), profiles of ozone, temperature, and pressure. JPL06 kinetics are used as a priori in the optimal estimation and for all other chemistry in the forward model. Using the more recent JPL09 kinetics results in insignificant differences in the retrieved value of J/kf. A complementary approach was used to derive the optimal kinetic parameters; the full parameter space of J, kf, Keq and ClOx was sampled to find the minimum in differences between measured and modelled ClO profiles. Furthermore, values of Keq up to 2.0 times larger than recommended by JPL06 were explored to test the sensitivity of the J/kf ratio to changes in Keq. The results show that the retrieved J/kf ratios bracket the range of 1.23 to 1.97 times the J/kf value recommended by JPL06 over the range of Keq values considered. The retrieved J/kf ratios lie in the lower half of the large uncertainty range of J/kf recommended by JPL06 and towards the upper portion of the smaller uncertainty range recommended by JPL09.
- ItemSolar cycle response and long-term trends in the mesospheric metal layers(Hoboken, NJ : Wiley, 2016) Dawkins, E.C.M.; Plane, J.M.C.; Chipperfield, M.P.; Feng, W.; Marsh, D.R.; Höffner, J.; Janches, D.The meteoric metal layers (Na, Fe, and K)—which form as a result of the ablation of incoming meteors—act as unique tracers for chemical and dynamical processes that occur within the upper mesosphere/lower thermosphere region. In this work, we examine whether these metal layers are sensitive indicators of decadal long-term changes within the upper atmosphere. Output from a whole-atmosphere climate model is used to assess the response of the Na, K, and Fe layers across a 50 year period (1955–2005). At short timescales, the K layer has previously been shown to exhibit a very different seasonal behavior compared to the other metals. Here we show that this unusual behavior is also exhibited at longer timescales (both the ~11 year solar cycle and 50 year periods), where K displays a much more pronounced response to atmospheric temperature changes than either Na or Fe. The contrasting solar cycle behavior of the K and Na layers predicted by the model is confirmed using satellite and lidar observations for the period 2004–2013.
- ItemResolving the strange behavior of extraterrestrial potassium in the upper atmosphere(Hoboken, NJ : Wiley, 2014) Plane, J.M.C.; Feng, W.; Dawkins, E.; Chipperfield, M.P.; Höffner, J.; Janches, D.; Marsh, D.R.It has been known since the 1960s that the layers of Na and K atoms, which occur between 80 and 105 km in the Earth's atmosphere as a result of meteoric ablation, exhibit completely different seasonal behavior. In the extratropics Na varies annually, with a pronounced wintertime maximum and summertime minimum. However, K varies semiannually with a small summertime maximum and minima at the equinoxes. This contrasting behavior has never been satisfactorily explained. Here we use a combination of electronic structure and chemical kinetic rate theory to determine two key differences in the chemistries of K and Na. First, the neutralization of K+ ions is only favored at low temperatures during summer. Second, cycling between K and its major neutral reservoir KHCO3 is essentially temperature independent. A whole atmosphere model incorporating this new chemistry, together with a meteor input function, now correctly predicts the seasonal behavior of the K layer.
- ItemFirst global observations of the mesospheric potassium layer(Hoboken, NJ : Wiley-Blackwell Publishing Ltd, 2014) Dawkins, E.C.M.; Plane, J.M.C.; Chipperfield, M.P.; Feng, W.; Gumbel, J.; Hedin, J.; Höffner, J.; Friedman, J.S.Metal species, produced by meteoric ablation, act as useful tracers of upper atmosphere dynamics and chemistry. Of these meteoric metals, K is an enigma: at extratropical latitudes, limited available lidar data show that the K layer displays a semiannual seasonal variability, rather than the annual pattern seen in other metals such as Na and Fe. Here we present the first near-global K retrieval, where K atom number density profiles are derived from dayglow measurements made by the Optical Spectrograph and Infrared Imager System spectrometer on board the Odin satellite. This robust retrieval produces density profiles with typical layer peak errors of ±15% and a 2km vertical grid resolution. We demonstrate that these retrieved profiles compare well with available lidar data and show for the first time that the unusual semiannual behavior is near-global in extent. This new data set has wider applications for improving understanding of the K chemistry and of related upper atmosphere processes. Key Points First quantitative retrieval of the terrestrial K layer from space The unusual semiannual behavior of K is near global in extent.