The present work describes the first fully automated method, based on on-line solid-phase extraction (SPE)-liquid chromatography-electrospray-tandem mass spectrometry, developed for the determination of drugs of abuse (17 compounds and metabolites belonging to the classes of amphetaminics, cannabinoids, cocainics, opiates, and lysergics) in sewage waters. On-line SPE is performed by passing 5 mL of the water sample through a PLRP-s cartridge for analytes measured in positive ionization mode (all but cannabinoids) and through an Oasis HLB cartridge for analytes measured in negative ionization mode (cannabinoids). For unequivocal identification and confirmation two selected reaction monitoring transitions are registered per compound, thus achieving the four identification points requested by the European Union for banned substances. Quantitation is performed by the internal standard method, indispensable to correct for matrix effects. The main advantages of the method developed are high sensitivity (limits of determination between 0.69 and 5.97 ng/L), selectivity and reliability of results, minimum sample manipulation, full automation, and fairly high throughput (analysis time per sample is 2 x 35 min). As a part of the validation procedure, the method developed has been applied to the analysis of various influent and effluent samples from four Spanish sewage treatment plants.

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Since the 1980s, brominated flame retardants (BFRs) have been detected in air, sewage sludge, sediment, fish, shellfish, birds, and mammals, including humans. However, model studies regarding BFR food-chain accumulation are scarce. In the present study, the accumulation of hexabromocyclododecane and brominated diphenyl ethers (BDEs) 47, 153, 154, and 183 in benthivorous barbel (Barbus graellsii) and pelagic bleak (Alburnus alburnus) from four locations in the Ebro river basin in Spain was modeled using a first-order, one-compartment model with sediment interaction. The model accounted for BFR uptake from water, ingested sediment, and food; release via water and feces; growth; and in situ binding of BFRs to black carbon. Rate constants were derived from allometric regressions. For most BFRs, dynamically modeled biota-sediment accumulation factors (BSAFs) were close to measured values, whereas steady-state model BSAFs were too high, especially for BDEs 153, 154, and 183. Differences between BSAFs for individual fish were explained by differences in age, growth, and feeding behavior. On average, modeled BSAFs for barbel were 50% higher than those for bleak because of extra BFR uptake through sediment ingestion and older age of barbel specimens.