Solid-phase extraction followed by liquid chromatography-time-of-flight-mass spectrometry to evaluate pharmaceuticals in effluents. A pilot monitoring study

The present work provides a multi-residue analytical method for determining a selection of 20 pharmaceuticals from diverse therapeutical classes in hospital effluent wastewater. The method is based on the simultaneous extraction of the target compounds by solid phase extraction (SPE), followed by liquid chromatography-time-of-flight-mass spectrometry (LC-TOF-MS) analysis. Using TOF-MS, accurate mass measurements within 2 ppm error were obtained for most of the pharmaceuticals studied. Empirical formula information can be obtained by this method, allowing the unequivocal identification of the target compounds in the samples. Validation studies showed that LC-TOF-MS analysis is a valuable new tool for identification and quantification of pharmaceuticals in wastewater. Recoveries, using Oasis HLB cartridges at pH 7, were higher than 75% for all pharmaceuticals, except for ranitidine, 4-methylaminoantipyrine (4-MAA), cefotaxime and omeprazole, which needed specific pH conditions for their extraction. Linearity of response over two orders of magnitude was demonstrated (r > 0.99). Matrix effects resulting in suppression of the response were observed. For most of the compounds ion suppression was less than 39%, except for metronidazole, carbamazepine 10,11-epoxide, naproxen and erythromycin, where the signal suppression was 42%, 59%, 46% and 95%, respectively. A simple and effective approach to minimize or avoid matrix interferences was the 1 : 4 dilution of the SPE extracts. Method detection limits (MDLs) and quantification limits (MQLs) ranged between 4-115 ng l(-1) and 14-384 ng l(-1), respectively. The precision of the method, calculated as relative standard deviation (RSD), ranged from 1.1-19.8% and 1.7-21.7% for intra- and inter-day, respectively. The developed analytical method was applied to the analysis of hospital effluent wastewater during a survey study. 18 of the 20 pharmaceuticals studied were detected at concentration levels of microg l(-1), reaching in some cases concentrations over 100 microg l(-1), and in the case of the analgesic and antipyretic dipyrone metabolite, higher than 1000 microg l(-1).     

Application of Synchronous Fluorescence Spectroscopy for Characterization of the Aromatic Hydrocarbons in Sediments of the Middle Adriatic

UV-fluorescence spectroscopy method with synchronous mode of scanning was used to characterize the types of aromatic hydrocarbons in surface sediments. the sampling stations were located on two transverses between Yugoslavian and the Italian coasts in the middle of the Adriatic Sea. the preparation of sediment samples was made according to IOC/UNESCO (1982). Synchronous excitation/emission scanning were done at wavelengths from 236/260 to 516/540 nm. Since the wavelength of maximum emission is a function of fused aromatic rings in a molecule, the fluorescence spectra of each sample were divided into three intervals: 300-340, 340-400, over 400 nm, corresponding to compounds with 2, 3 and 4,5 and more rings respectively.

Large qualitative differences were established between sediment samples. PAH with 5 and more rings are more prevalent near the Italian coast.     

Copper-algae interactions: Inheritance or adaptation?

This study evaluated the responses of wild, adult plants of Enteromorpha compressa, and their progeny, to various copper concentrations. Experiments were designed to test the hypotheses that: 1) individuals of E. compressa from Caleta Palito, a copper-enriched coastal locality, tolerate higher copper concentrations than those from a place with no history of copper pollution and 2) such copper tolerance is under genetic control and therefore, was an inherited character. Our results indicate that algae which inhabit a copper-enriched environment tolerate higher concentrations of copper than those from waters with low copper concentrations. On the other hand, our results suggest that generalizations regarding heritability of the tolerance to copper do not apply to the Chilean E. compressa, as no differences in growth or rhizoid production were found between the progeny from Caleta Palito and Caleta Zenteno. These findings are an indication that heritability and adaptation may represent alternative strategies used by different populations of the same algal species to tolerate copper.