Air-water transfer of MTBE, its degradation products, and alternative fuel oxygenates: the role of temperature.

The gasoline oxygenate methyl tert-butyl ether (MTBE) has become one of the world's mostwidespread groundwater and surface water contaminants. As a result, there has been increasing interest in the environmental behavior of MTBE and its degradation products, mainly tert-butyl formate (TBF) and tert-butyl alcohol (TBA). In contrast, the environmental behavior of the proposed alternatives to MTBE, namely ethyl tert-butyl ether (ETBE), tert-amyl methyl ether (TAME), and diisopropyl ether (DIPE) has hardly been studied yet, although some of them are already in substantial use in various countries. A key parameter for the assessment of the fate, transport, and possible remediation of these contaminants is the air-water partitioning constant (KiH). The KiH is highly temperature dependent, and it is therefore necessary to obtain reliable experimental values at relevant temperatures. Hence, the KiH of MTBE, ETBE, TAME, and DIPE, along with the degradation products, TBF and methyl acetate, were determined from 5 degrees C-40 degrees C. The alternatives to MTBE generally had a higher KiH, which implies that, upon emission into the environment, the alternatives partition more readily into the air phase than MTBE. This may favor their use, as it is in the air phase where dilution and degradation are the most effective. The degradation products of MTBE, with the exception of TBF, have much lower KiH values at all temperatures. Hence, the degradation products will have a stronger affinity for the water phase. The temperature dependency of the kinetics of air-watertransfer is discussed using a boundary layer model. Only for TBA but not for the ethers a significant effect of temperature was found.