Monitoring of the gasoline oxygenate MTBE and BTEX compounds in groundwater in Catalonia (northeast Spain).

Headspace (HS) gas chromatography with flame ionisation detection (HS-GC-FID) and purge and trap (P) gas chromatography-mass spectrometry (P) were used for the determination of methyl-tert-butyl ether (MTBE) and benzene, toluene, and xylenes (BTEX) in groundwater. In this work, we present the first data on the levels of MTBE and BTEX in different groundwater wells in the area of Catalonia (northeast Spain). This monitoring campaign corresponded to 28 groundwater wells that were located near petrol service stations, oil refinery storage tanks, and/or chemical industry at different locations of Catalonia during the period of 1998/1999. The levels of MTBE detected varied between 4-300 microg/l, but two sites had MTBE levels up to 3 and 13 mg/l. In many cases, the BTEX levels were below 1 microg/l, whereas 7 sites had levels varying from 19 microg/l up to 3 mg/l. Most of them were related to leakage from underground tanks in petrol service stations, while the remaining three corresponded respectively to chemical industrial pollution of undetermined origin and to a leak from high-ground petrol tanks in petrochemical refinery factories. The aquifers involved were constituted by detritus coarse materials, sands, and conglomerates. Piezometric levels were roughly comprised between 3 and 40 m, and permeability (K) and transmissivity (T) values were estimated from field measurements. The MTBE/BTEX ratio was also calculated and reached values up to 250. These values were expected, since if we consider that spilled oxygenated gasoline is the source of well contamination and based on solubility considerations alone, the MTBE source concentrations would be about 200 times higher than any BTEX compounds.

Fate of MTBE and DCPD compounds relative to BTEX in gasoline-contaminated aquifers.

The aim of this communication is to provide preliminary results on MTBE monitoring, and at the same time to propose some new tracers of gasoline pollution in groundwater. An overview is presented on benzene-toluene-ethylbenzene-xylene (BTEX), methyl tertiary-butyl ether (MTBE), and dicyclopentadienes (DCPD) contents in gasoline formulations. Their specific fate in gasoline-contaminated aquifers are consistent with their physical-chemical properties.

Determination of drugs in surface water and wastewater samples by liquid chromatography-mass spectrometry: methods and preliminary results including toxicity studies with Vibrio fischeri.

In the present work a combined analytical method involving toxicity and liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) was developed for the determination of pharmaceutical compounds in water samples. The drugs investigated were the analgesics: ibuprofen, ketoprofen, naproxen, and diclofenac, the decomposition product of the acetyl salicylic acid: salicylic acid and one lipid lowering agent, gemfibrozil. The selected compounds are acidic substances, very polar and all of them are analgesic compounds that can be purchased without medical prescription. The developed protocol consisted, first of all, on the use Microtox and ToxAlert 100 toxicity tests with Vibriofischeri for the different pharmaceutical drugs. The 50% effective concentration (EC50) values and the toxicity units (TU) were determined for every compound using both systems. Sample enrichment of water samples was achieved by solid-phase extraction procedure (SPE), using the Merck LiChrolut EN cartridges followed by LC-ESI-MS. Average recoveries loading 11 of samples with pH=2 varied from 69 to 91% and the detection limits in the range of 15-56 ng/l. The developed method was applied to real samples from wastewater and surface-river waters of Catalonia (north-east of Spain). One batch of samples was analyzed in parallel also by High Resolution Gas Chromatography coupled with Mass Spectrometry (HRGC-MS) and the results have been compared with the LC-ESI-MS method developed in this work.