Simultaneous determination of methyl tert.-butyl ether and its degradation products, other gasoline oxygenates and benzene, toluene, ethylbenzene and xylenes in Catalonian groundwater by purge-and-trap-gas chromatography–mass spectrometry

Abstract

In Catalonia (northeast Spain), a monitoring program was carried out to determine methyl tert.-butyl ether (MTBE), its main degradation products, tert.-butyl alcohol (TBA), tert.-butyl formate (TBF), and other gasoline additives, the oxygenate dialkyl ethers ethyl tert.-butyl ether, tert.-amyl methyl ether and diisopropyl ether and the aromatic compounds benzene, toluene, ethylbenzene and xylene (BTEX) in 21 groundwater wells that were located near different gasoline point sources (a gasoline spill and underground storage tank leakage). Purge-and-trap coupled to gas chromatography–mass spectrometry was optimised for the simultaneous determination of the above mentioned compounds and enabled to detect concentrations at ng/l or sub-μg/l concentrations. Special attention was given to the determination of polar MTBE degradation products, TBA and TBF, since not much data on method performance and environmental levels are given on these compounds in groundwater. All samples analysed contained MTBE at levels between 0.3 and 70 μg/l. Seven contaminated hot spots were identified with levels up to US Environmental Protection Agency drinking water advisory (20–40 μg/l) and a maximum concentration of 670 μg/l (doubling the Danish suggested toxicity level of 350 μg/l). Samples with high levels of MTBE contained 0.1–60 μg/l of TBA, indicating (but not proving) in situ degradation of parent compound. In all cases, BTEX was at low concentrations or not detected showing less solubility and persistence than MTBE. This fact confirms the suitability of MTBE as a tracer or indicator of long-term gasoline contamination than the historically used BTEX.