Mechanism of ozone loss under enhanced water vapour conditions in the mid-latitude lower stratosphere in summer

Abstract

Abstract. Water vapour convectively injected into the mid-latitude lowermost stratosphere could affect stratospheric ozone. The associated potential ozone loss process requires low temperatures together with elevated water vapour mixing ratios. Since this ozone loss is initiated by heterogeneous chlorine activation on liquid aerosols, an increase in sulfate aerosol surface area due to a volcanic eruption or geoengineering could increase the likelihood of its occurrence. However, the chemical mechanism of this ozone loss process has not yet been analysed in sufficient detail and its sensitivity to various conditions is not yet clear. Under conditions of climate change associated with an increase in greenhouse gases, both a stratospheric cooling and an increase in water vapour convectively injected into the stratosphere are expected. Understanding the influence of low temperatures, elevated water vapour and enhanced sulfate particles on this ozone loss mechanism is a key step in estimating the impact of climate change and potential sulfate geoengineering on mid-latitude ozone. Here, we analyse the ozone loss mechanism and its sensitivity to various stratospheric conditions in detail. By conducting a box-model study with the Chemical Lagrangian Model of the Stratosphere (CLaMS), chemistry was simulated along a 7 d backward trajectory. This trajectory was calculated neglecting mixing of neighbouring air masses. Chemical simulations were initialized using measurements taken during the Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) aircraft campaign (2013, Texas), which encountered an elevated water vapour mixing ratio of 10.6 ppmv at a pressure level around 100 hPa. We present a detailed analysis of the ozone loss mechanism, including the chlorine activation, chlorine-catalysed ozone loss cycles, maintenance of activated chlorine and the role of active nitrogen oxide radicals (NOx). Focussing on a realistic trajectory in a temperature range from 197 to 202 K, a threshold in water vapour of 10.6 ppmv has to be exceeded and maintained for stratospheric ozone loss to occur. We investigated the sensitivity of the water vapour threshold to temperature, sulfate content, inorganic chlorine (Cly), inorganic nitrogen (NOy) and inorganic bromine (Bry). The water vapour threshold is mainly determined by the temperature and sulfate content. However, the amount of ozone loss depends on Cly, Bry and the duration of the time period over which chlorine activation can be maintained. NOy affects both the potential of ozone formation and the balance between reactions yielding chlorine activation and deactivation, which determines the water vapour threshold. Our results show that in order to deplete ozone, a chlorine activation time of 24 to 36 h for conditions of the water vapour threshold with low temperatures must be maintained. A maximum ozone loss of 9 % was found for a 20 ppmv water vapour mixing ratio using North American Monsoon (NAM) tropopause standard conditions with a chemical box-model simulation along a realistic trajectory. For the same trajectory, using observed conditions (of 10.6 ppmv H2O), the occurrence of simulated ozone loss was dependent on the sulfate amount assumed. Detailed analysis of current and future possibilities is needed to assess whether enhanced water vapour conditions in the summertime mid-latitude lower stratosphere lead to significant ozone loss.