Abstract
The aqueous environmental fate of two antibiotics, lincomycin and clarithromycin, and an antiepileptic drug, carbamazepine, was investigated by monitoring drugs decomposition and identifying intermediates in Po river water (North Italy). Initially, control experiments in the dark and under illumination were performed on river water spiked with drugs to simulate all possible transformation processes occurring in the aquatic system. Under illumination, these pharmaceuticals were degraded and transformed into numerous organic intermediate compounds. Several species were formed and characterised by analysing MS and MSn spectra and by comparison with parent molecule fragmentation pathways. River water was sampled at three sampling points in an urban area. The selected pharmaceuticals were detected in all samples. Eight transformation products identified in the laboratory simulation were found in natural river water from carbamazepine degradation, three from clarithromycin and two from lincomycin. Their transformation occurring in aquatic system mainly involved mono- and poly-hydroxylation followed by oxidation of the hydroxyl groups.
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References
Andreozzi R, Marotta R, Nicklas P (2003) Pharmaceuticals in STP effluents and their solar photodegradation in aquatic environment. Chemosphere 50(10):1319–1330
Bottoni P, Fidente R (2005) Un primo contributo alla problematica dei farmaci come contaminanti delle acque. Ann Ist Super Sanità 41(3):333–342
Boule P, Bahenmann DW, Robertson DW, Robertson PKJ (2005) The handbook of environmental chemistry. Springer, Berlin
Breton H, Cociglio M, Bressolle F, Peyriere H, Blayac JP, Hillaire-Buys D (2005) Liquid chromatography–electrospray mass spectrometry determination of carbamazepine, oxcarbazepine and eight of their metabolites in human plasma. J Chromatogr B 828:80–90
Calamari D, Zuccato E, Castiglioni S, Bagnati R, Fanelli R (2003) Strategic survey of therapeutic drugs in the river Po and Lambro in northern Italy. Environ Sci Technol 37(7):1241–1248
Calza P, Medana C, Pazzi M, Baiocchi C, Pelizzetti E (2004) The photocatalytic process as a tool to identify metabolitic products formed from dopant substances: the case of buspirone. J Pharmaceut Biomed Anal 35(1):9–19
Calza P, Marchisio S, Medana C, Baiocchi C (2010) Fate of antibacterial spiramycin in river waters. Anal Bioanal Chem 396(4):1539–1550
Calza P, Medana C, Raso E, Giancotti V, Minero C (2011) N,N-diethyl-m-toluamide transformation in river water. Sci Tot Environ 409:3894–3901
Calza P, Medana C, Padovano E, Dal BF, Baiocchi C (2012a) Identification of the unknown transformation products derived from lincomycin using LCHR-MS technique. J Mass Spectrom 47:751–759
Calza P, Medana C, Padovano E, Giancotti V, Baiocchi C (2012b) Identification of the unknown transformation products derived from clarithromycin and carbamazepine using LCHR-MS technique. Rapid Comm Mass Spectrom 26(15):1687–1704
Castiglioni S, Fanelli R, Calamari D, Bagnati R, Zuccato E (2004) Methodological approaches for studying pharmaceuticals in the environment by comparing predicted and measured concentrations in River Po, Italy. Regul Toxicol Pharm 39(1):25–32
Castiglioni S, Bagnati R, Calamari D, Fanelli R, Zuccato E (2005) A multiresidue analytical method using solid-phase extraction and high-pressure liquid chromatography tandem mass spectrometry to measure pharmaceuticals of different therapeutic classes in urban wastewaters. J Chromatogr A 1092(2):206–215
Daughton CG (2001) Emerging pollutants, and communicating the science of environmental chemistry and mass spectrometry: pharmaceuticals in the environment. J Am Soc Mass Spectrom 12(10):1067–1076
Daughton CG, Ternes T (1999) Pharmaceuticals and Personal care products in the environment: agent of subtle change? Environ Health Pers 107(6):907–938
De Laurentiis E, Chiron S, Kouras-Hadef S, Richard C, Minella M, Maurino V, Minero C, Vione D. Photochemical fate of carbamazepine in surface waters: laboratory measures and modeling. Environ Sci Technol 2012; (in press)
Heberer T, Reddersen K, Mechlinski A (2002) From municipal sewage in drinking water: fate and removal of pharmaceuticals residues in the aquatic environment in urban areas. Water Sci Technol 46:81–88
Khetan SK, Collins TJ (2007) Human Pharmaceuticals in the environment: a challenge to green chemistry. Chem Rev 107(6):2319–2364
Kummerer K (2004) Resistance in the environment. J Antimicrob Chemother 54(2):311–320
Maggs JL, Pirmohamed M, Kitteringham NR, Park BK (1996) Characterization of the metabolites of carbamazepine in patient urine by liquid chromatography/mass spectrometry. Drug Metab Dispos 25(3):275–280
Miao XS, Yang JJ, Metcalfe CD (2003) Determination of carbamazepine and its metabolites in aqueous samples using liquid chromatography–electrospray tandem mass spectrometry. Anal Chem 75(15):3731–3738
Miao XS, Yang JJ, Metcalfe CD (2005) Carbamazepine and its metabolites in wastewater and in biosolids in a municipal wastewater treatment plant. Environ Sci Technol 39(19):7469–7475
Petrovic M, Barcelò D (2007) LC-MS for identifying photodegradation products of pharmaceuticals in the environment. Trend Anal Chem 26(6):486–493
Richardson SD, Ternes TA (2011) Water analysis: emerging contaminants and current issues. Anal Chem 83:4614–4648
Zuccato E, Calamari D, Natangelo M, Fanelli R (2000) Presence of therapeutic drugs in the environment. Lancet 355(9217):1789–1790
Zuccato E, Castiglioni S, Fanelli R (2005) Identification of the pharmaceuticals for human use contaminating the Italian aquatic environment. J Hazard Mater 122(3):205–209
Zuccato E, Castiglioni S, Fanelli R, Reitano G, Bagnati R, Chiabrando C, Pomati F, Rossetti C, Calamari D (2006) Pharmaceuticals in the environment in Italy: causes, occurrence, effects and control. Environ Eng Sci 13(1):15–21
Zuccato E, Castiglioni S, Bagnati R, Melis M, Fanelli R (2010) Source, occurrence and fate of antibiotics in the Italian aquatic environment. J Hazard Mater 179(2):1042–1048
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Calza, P., Medana, C., Padovano, E. et al. Fate of selected pharmaceuticals in river waters. Environ Sci Pollut Res 20, 2262–2270 (2013). https://doi.org/10.1007/s11356-012-1097-4
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DOI: https://doi.org/10.1007/s11356-012-1097-4