Stratospheric dynamics and midlatitude jets under geoengineering with space mirrors and sulfate and titania aerosols

The impact on the dynamics of the stratosphere of three approaches to geoengineering by solar radiation management is investigated using idealized simulations of a global climate model. The approaches are geoengineering with sulfate aerosols, titania aerosols, and reduction in total solar irradiance (representing mirrors placed in space). If it were possible to use stratospheric aerosols to counterbalance the surface warming produced by a quadrupling of atmospheric carbon dioxide concentrations, tropical lower stratospheric radiative heating would drive a thermal wind response which would intensify the stratospheric polar vortices. In the Northern Hemisphere this intensification results in strong dynamical cooling of the polar stratosphere. Northern Hemisphere stratospheric sudden warming events become rare (one and two in 65 years for sulfate and titania, respectively). The intensification of the polar vortices results in a poleward shift of the tropospheric midlatitude jets in winter. The aerosol radiative heating enhances the tropical upwelling in the lower stratosphere, influencing the strength of the Brewer-Dobson circulation. In contrast, solar dimming does not produce heating of the tropical lower stratosphere, and so there is little intensification of the polar vortex and no enhanced tropical upwelling. The dynamical response to titania aerosol is qualitatively similar to the response to sulfate.

Model catalyst studies of the strong metal-support interaction: Surface structure identified by STM on Pd nanoparticles on TiO2(110)

Model catalysts of Pd nanoparticles and films on TiO2 (I 10) were fabricated by metal vapour deposition (MVD). Molecular beam measurements show that the particles are active for CO adsorption, with a global sticking probability of 0.25, but that they are deactivated by annealing above 600 K, an effect indicative of SMSI. The Pd nanoparticles are single crystals oriented with their (I 11) plane parallel to the surface plane of the titania. Analysis of the surface by atomic resolution STM shows that new structures have formed at the surface of the Pd nanoparticles and films after annealing above 800 K. There are only two structures, a zigzag arrangement and a much more complex "pinwheel" structure. The former has a unit cell containing 7 atoms, and the latter is a bigger unit cell containing 25 atoms. These new structures are due to an overlayer of titania that has appeared on the surface of the Pd nanoparticles after annealing, and it is proposed that the surface layer that causes the SMSI effect is a mixed alloy of Pd and Ti, with only two discrete ratios of atoms: Pd/Ti of 1: 1 (pinwheel) and 1:2 (zigzag). We propose that it is these structures that cause the SMSI effect. (c) 2005 Elsevier Inc. All rights reserved.

The role of Ti3+ interstitials in TiO2(110) reduction and oxidation

Here we describe results which teach us much about the mechanism of the reduction and oxidation of TiO2(110) by the application of scanning tunnelling microscopy imaging at high temperatures. Titania reduces at high temperature by thermal oxygen loss to leave localized (i.e. Ti3+) and delocalized electrons on the lattice Ti, and a reduced titania interstitial that diffuses into the bulk of the crystal. The interstitial titania can be recalled to the surface by treatment in very low pressures of oxygen, occurring at a significant rate even at 573 K. This re-oxidation occurs by re-growth of titania layers in a Volmer-Weber manner, by a repeating sequence in which in-growth of extra titania within the cross-linked (1 x 2) structure completes the (1 x 1) bulk termination. The next layer then initiates with the nucleation of points and strings which extend to form islands of cross-linked (1 x 2), which once again grow and fill in to reform the (1 x 1). This process continues in a cyclical manner to form many new layers of well-ordered titania. The details of the mechanism and kinetics of the process are considered.

Stratospheric heating by potential geoengineering aerosols

A fixed dynamical heating model is used to investigate the pattern of zonal-mean stratospheric temperature change resulting from geoengineering with aerosols composed of sulfate, titania, limestone and soot. Aerosol always heats the tropical lower stratosphere, but at the poles the response can be either heating, cooling, or neutral. The sign of the change in stratospheric Pole-Equator temperature difference depends on aerosol type, size and season. This has implications for modelling geoengineering impacts and the response of the stratospheric circulation.