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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.
- ItemPlanetary geostrophic equations for the atmosphere with evolution of the barotropic flow(Amsterdam : Elsevier, 2009) Dolaptchiev, S.I.; Klein, R.Atmospheric phenomena such as the quasi-stationary Rossby waves, teleconnection patterns, ultralong persistent blockings and the polar/subtropical jet are characterized by planetary spatial scales, i.e. scales of the order of the earth's radius. This motivates our interest in the relevant physical processes acting on the planetary scales. Using an asymptotic approach, we systematically derive reduced model equations valid for atmospheric motions with planetary spatial scales and a temporal scale of the order of about 1 week. We assume variations of the background potential temperature comparable in magnitude with those adopted in the classical quasi-geostrophic theory. At leading order, the resulting equations include the planetary geostrophic balance. In order to apply these equations to the atmosphere, one has to prescribe a closure for the vertically averaged pressure. We present an evolution equation for this component of the pressure which was derived in a systematic way from the asymptotic analysis. Relative to the prognostic closures adopted in existing reduced-complexity planetary models, this new dynamical closure may provide for more realistic increased large-scale, long-time variability in future implementations. © 2008 Elsevier B.V. All rights reserved.