Reactive hydro- and chlorocarbons in the troposphere and lower stratosphere : sources, distributions, and chemical impact

Abstract

The work presented in this thesis focuses on measurements of chemical reactive C2 C7 non-methane hydrocarbons (NMHC) and C1 C2 chlorocarbons with atmospheric lifetimes of a few hours up to about a year. The group of reactive chlorocarbons includes the most abundant atmospheric species with large natural sources, which are chloromethane (CH3Cl), dichloromethane (CH2Cl2), and trichloromethane (CHCl3), and tetrachloroethylene (C2Cl4) with mainly anthropogenic sources. The NMHC and chlorocarbons are present at relatively low quantities in our atmosphere (10-12 10-9 mol mol-1 of air). Nevertheless, they play a key role in atmospheric photochemistry. For example, the oxidation of NMHC plays a dominant role in the formation of ozone in the troposphere, while the photolysis of chlorocarbons contributes to enhanced ozone depletion in the stratosphere. In spite of their important role, however, their global source and sinks budgets are still poorly understood. Hence, this study aims at improving our understanding of the sources, distribution, and chemical role of reactive NMHC and chlorocarbons in the troposphere and lower stratosphere. To meet this aim, a comprehensive data set of selected C2 C7 NMHC and chlorocarbons has been analyzed, derived from six aircraft measurement campaigns with two different jet aircrafts (the Dutch TUD/NLR Cessna Citation PH-LAB, and the German DLR Falcon) conducted between 1995 and 2001 (STREAM 1995 and 1997 and 1998, LBA-CLAIRE 1998, INDOEX 1999, MINOS 2001). The NMHC and chlorocarbons have been detected by gas-chromatography (GC-FID/ECD) in pre-concentrated whole air samples collected in stainless steel canister on-board the measurement aircrafts. The measurement locations include tropical (Maldives/Indian Ocean and Surinam), midlatitude (Western Europe and Canada) and polar regions (Lapland/northern Sweden) between the equator to about 70ºN, covering different seasons and pollution levels in the troposphere and lower stratosphere. Of special interest in this thesis are the tropical regions because they are becoming increasingly important in terms of global anthropogenic pollution and climate change. In addition, natural emissions of hydrocarbons (notably isoprene and terpenes from plants) and reactive chlorocarbons appear to be concentrated in the tropics, where the largest uncertainties exist with respect to source type and source strength. Whenever available, the reactive NMHC and chlorocarbon data have been analyzed with the help of concurrent measurements, which includes ozone (O3), carbon monoxide (CO), nitrogen oxide (NO), total reactive oxidized nitrogen (NOy), nitrous oxide (N2O), carbon dioxide (CO2), methane (CH4), acetone (CH3COCH3), methanol (CH3OH), acetonitrile (CH3CN), the chlorofluorocarbons CFC-11 (CCl3F) and CFC-12 (CCl2F2), the hydrofluorocarbon HFC-134a (CH2FCF3), and the hydrochlorofluorocarbons HCFC-141b (CH3CCl2F) and HCFC-142b (CH3CClF2). These additional measurements provided important information about the air mass origin, pollution sources, and chemical age of the encountered air masses. The STREAM-measurements contribute to the present understanding of the budgets of reactive organic trace species in the mid-latitude lower stratosphere at different seasonal conditions. It was found that during summer and fall, the mean concentrations of reactive NMHC and acetone in the lower stratosphere were a factor of two or more higher than during winter, as a result of more intense and frequent mixing across the tropopause. The role of tropical emissions in the global budget of hydrocarbons and the chlorocarbons CH3Cl, CH2Cl2, CHCl3, and C2Cl4 has been investigated during the LBA/CLAIRE 1998, INDOEX 1999 and MINOS 2001 campaigns. The INDOEX measurements over the Indian Ocean showed that strongly enhanced CH3Cl and related combustion tracers, such as CO, hydrocarbons and CH3CN in polluted air masses from India and Southeast Asia, relate to the extensive use of biofuels (notably the burning of agricultural waste and dung) in households and small industries. During the MINOS campaign it was found that deep convection associated with the Asian summer monsoon followed by long-range transport carries Asian pollution towards the eastern Mediterranean and northern Africa, thus affecting tropospheric chemistry on a hemispheric scale. Enhanced levels of CO, and hydrocarbons in Asian pollution were found to be comparable to or higher than those found in westerly air masses, containing pollution from the North American continent. It is expected that the increasing use of fossil fuel in Asia will enhance photochemical ozone formation in the Asian plume in the future. This is important because ozone acts as an effective greenhouse gas near the tropopause. Based on measurements performed over the Surinam rainforest during LBA-CLAIRE it is concluded that tropical forests are the most important source of organic chlorine, mainly in the form of CH3Cl, to the atmosphere. It is shown that the reduction of tropical forest area over the past 20 years could largely explain the observed downward trend in atmospheric CH3Cl