[1] We report the first empirical quantification of the relation between winter-spring loss of Arctic ozone and changes in stratospheric climate. Our observations show that $15 DU additional loss of column ozone can be expected per Kelvin cooling of the Arctic lower stratosphere, an impact nearly three times larger than current model simulations suggest. We show that stratospheric climate conditions became significantly more favorable for large Arctic ozone losses over the past four decades; i.e., the maximum potential for formation of polar stratospheric clouds increased steadily by a factor of three. Severe Arctic ozone loss during the past decade occurred as a result of the combined effect of this long-term climate change and the anthropogenic increase in stratospheric halogens.

Large particles containing nitric acid (HNO3) were observed in the 1999/2000 Arctic winter stratosphere. These in situ observations were made over a large altitude range (16 to 21 kilometers) and horizontal extent (1800 kilometers) on several airborne sampling flights during a period of several weeks. With diameters of 10 to 20 micrometers, these sedimenting particles have significant potential to denitrify the lower stratosphere. A microphysical model of nitric acid trihydrate particles is able to simulate the growth and sedimentation of these large sizes in the lower stratosphere, but the nucleation process is not yet known. Accurate modeling of the formation of these large particles is essential for understanding Arctic denitrification and predicting future Arctic ozone abundances.

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[1] Measurements of BrO suggest that inorganic bromine (Br y ) at and above the tropopause is 4 to 8 ppt greater than assumed in models used in past ozone trend assessment studies. This additional bromine is likely carried to the stratosphere by short-lived biogenic compounds and their decomposition products, including tropospheric BrO. Including this additional bromine in an ozone trend simulation increases the computed ozone depletion over the past $25 years, leading to better agreement between measured and modeled ozone trends. This additional Br y (assumed constant over time) causes more ozone depletion because associated BrO provides a reaction partner for ClO, which increases due to anthropogenic sources. Enhanced Br y causes photochemical loss of ozone below $14 km to change from being controlled by HO x catalytic cycles (primarily HO 2 +O 3 ) to a situation where loss by the BrO+HO 2 cycle is also important. Citation: Salawitch, R. J.,

[1] The Arctic polar vortex exhibited widespread regions of low temperatures during the winter of 2005, resulting in significant ozone depletion by chlorine and bromine species. We show that chemical loss of column ozone (DO 3 ) and the volume of Arctic vortex air cold enough to support the existence of polar stratospheric clouds (V PSC ) both exceed levels found for any other Arctic winter during the past 40 years. Cold conditions and ozone loss in the lowermost Arctic stratosphere (e.g., between potential temperatures of 360 to 400 K) were particularly unusual compared to previous years. Measurements indicate DO 3 = 121 ± 20 DU and that DO 3 versus V PSC lies along an extension of the compact, near linear relation observed for previous Arctic winters. The maximum value of V PSC during five to ten year intervals exhibits a steady, monotonic increase over the past four decades, indicating that the coldest Arctic winters have become significantly colder, and hence are more conducive to ozone depletion by anthropogenic halogens.

The large burden of sulfate aerosols injected into the stratosphere by the eruption of Mount Pinatubo in 1991 cooled Earth and enhanced the destruction of polar ozone in the subsequent few years. The continuous injection of sulfur into the stratosphere has been suggested as a "geoengineering" scheme to counteract global warming. We use an empirical relationship between ozone depletion and chlorine activation to estimate how this approach might influence polar ozone. An injection of sulfur large enough to compensate for surface warming caused by the doubling of atmospheric CO2 would strongly increase the extent of Arctic ozone depletion during the present century for cold winters and would cause a considerable delay, between 30 and 70 years, in the expected recovery of the Antarctic ozone hole.

Higher temperatures caused by increasing greenhouse gas concentrations are predicted to exacerbate photochemical smog if precursor emissions remain constant. We perform a statistical analysis of 21 years of ozone and temperature observations across the rural eastern U.S. The climate penalty factor is defined as the slope of the ozone/temperature relationship. For two precursor emission regimes, before and after 2002, the climate penalty factor was consistent across the distribution of ozone observations. Prior to 2002, ozone increased by an average of ∼3.2 ppbv/°C. After 2002, power plant NOx emissions were reduced by 43%, ozone levels fell ∼10%, and the climate penalty factor dropped to ∼2.2 ppbv/°C. NOx controls are effective for reducing photochemical smog and might lessen the severity of projected climate change penalties. Air quality models should be evaluated against these observations, and the climate penalty factor metric may be useful for evaluating the response of ozone to climate change.

Abstract. Very short-lived (VSL) bromocarbons are produced at a prodigious rate by ocean biology and these source compounds (SGVSL), together with their inorganic degradation products (PGVSL), are lofted by vigorous convection to the tropical tropopause layer (TTL). Using a state-of-the-art photochemical mechanism within a global model, we calculate annual average stratospheric injection of total bromine due to VSL sources to be 5 pptv (parts per trillion by volume), with ~ 3 pptv entering the stratosphere as PGVSL and ~ 2 pptv as SGVSL. The geographic distribution and partitioning of VSL bromine within the TTL, and its consequent stratospheric injection, is highly dependent on the oceanic flux, the strength of convection and the occurrence of heterogeneous recycling reactions. Our calculations indicate atomic Br should be the dominant inorganic species in large regions of the TTL during daytime, due to the low ozone and cold conditions of this region. We propose the existence of a "tropical ring of atomic bromine" located approximately between 15 and 19 km and between 30° N and 30° S. Daytime Br / BrO ratios of up to ~ 4 are predicted within this inhomogeneous ring in regions of highly convective transport, such as the tropical Western Pacific. Therefore, we suggest that experimental programs designed to quantify the bromine budget of the TTL and the stratospheric injection of VSL biogenic bromocarbons should include a strategy for the measurement of atomic Br during daytime as well as HOBr and BrCl during nighttime.