Abstract
Comprehensive source and fate studies of pharmaceuticals in the environment require analytical methods able to quantify a wide range of molecules over various therapeutic classes, in aqueous and solid matrices. Considering this need, the development of an analytical method to determine 53 pharmaceuticals in aqueous phase and in solid matrices using a combination of microwave-assisted extraction, solid phase extraction, and liquid chromatography coupled with tandem mass spectrometry is reported. Method was successfully validated regarding linearity, repeatability, and overall protocol recovery. Method detection limits (MDLs) do not exceed 1 ng L−1 for 40 molecules in aqueous matrices (6 ng L−1 for the 13 remaining), while subnanogram per gram MDLs were reached for 38 molecules in solid phase (29 ng g−1 for the 15 remaining). Losses due to preparative steps were assessed for the 32 analytes associated to their labeled homologue, revealing an average loss of 40 % during reconcentration, the most altering step. Presence of analytes in wastewater treatment plant (WWTP) effluent aqueous phase and suspended solids (SS) as well as in river water, SS, and sediments was then investigated on a periurban river located in the suburbs of Bordeaux, France, revealing a major contribution of WWTP effluent to the river contamination. Sorption on river SS exceeded 5 % of total concentration for amitriptyline, fluoxetine, imipramine, ritonavir, sildenafil, and propranolol and appeared to be submitted to a seasonal influence. Sediment contamination was lower than the one of SS, organic carbon content, and sediment fine element proportion was accountable for the highest measured concentrations.
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References
Daughton CG, Ternes TA (1999) Pharmaceuticals and personal care products in the environment: agents of subtle change? Environ Health Perspect 107:907–938
Fatta-Kassinos D, Meric S, Nikolaou A (2011) Pharmaceutical residues in environmental waters and wastewater: current state of knowledge and future research. Anal Bioanal Chem 399:251–275
Kasprzyk-Hordern B, Dinsdale RM, Guwy AJ (2008) The occurrence of pharmaceuticals, personal care products, endocrine disruptors and illicit drugs in surface water in South Wales, UK. Water Res 42:3498–3518
Togola A, Budzinski H (2008) Multi-residue analysis of pharmaceutical compounds in aqueous samples. J Chromatogr A 1177:150–158
Gabet-Giraud V, Miège C, Choubert JM, Ruel SM, Coquery M (2010) Occurrence and removal of estrogens and beta blockers by various processes in wastewater treatment plants. Sci Total Environ 408:4257–4269
Lajeunesse A, Smyth SA, Barclay K, Sauvé S, Gagnon C (2012) Distribution of antidepressant residues in wastewater and biosolids following different treatment processes by municipal wastewater treatment plants in Canada. Water Res 46:5600–5612
Teerlink J, Hering AS, Higgins CP, Drewes JE (2012) Variability of trace organic chemical concentrations in raw wastewater at three distinct sewershed scales. Water Res 46:3261–3271
Bayen S, Zhang H, Desai MM, Ooi SK, Kelly BC (2013) Occurrence and distribution of pharmaceutically active and endocrine disrupting compounds in Singapore’s marine environment: influence of hydrodynamics and physical-chemical properties. Environ Pollut 182:1–8
Quintana JB, Weiss S, Reemtsma T (2005) Pathways and metabolites of microbial degradation of selected acidic pharmaceutical and their occurrence in municipal wastewater treated by a membrane bioreactor. Water Res 39:2654–2664
Rosal R, Rodríguez A, Perdigón-Melón JA, Petre A, García-Calvo E, Gómez MJ, Agüera A, Fernández-Alba AR (2010) Occurrence of emerging pollutants in urban wastewater and their removal through biological treatment followed by ozonation. Water Res 44:578–588
Martin Ruel S, Esperanza M, Choubert J-M, Valor I, Budzinski H, Coquery M (2010) On-site evaluation of the efficiency of conventional and advanced secondary processes for the removal of 60 organic micropollutants. Water Sci Technol 62:2970–2978
Benotti MJ, Brownawell BJ (2007) Distributions of pharmaceuticals in an urban estuary during both dry- and wet-weather conditions. Environ Sci Technol 41:5795–5802
Kunkel U, Radke M (2012) Fate of pharmaceuticals in rivers: deriving a benchmark dataset at favorable attenuation conditions. Water Res 46:5551–5565
Baker DR, Kasprzyk-Hordern B (2011) Multi-residue determination of the sorption of illicit drugs and pharmaceuticals to wastewater suspended particulate matter using pressurised liquid extraction, solid phase extraction and liquid chromatography coupled with tandem mass spectrometry. J Chromatogr A 1218:7901–7913
da Silva BF, Jelic A, López-Serna R, Mozeto AA, Petrovic M, Barceló D (2011) Occurrence and distribution of pharmaceuticals in surface water, suspended solids and sediments of the Ebro river basin, Spain. Chemosphere 85:1331–1339
Burke V, Treumann S, Duennbier U, Greskowiak J, Massmann G (2013) Sorption behavior of 20 wastewater originated micropollutants in groundwater—column experiments with pharmaceutical residues and industrial agents. J Contam Hydrol 154:29–41
Bones J, Thomas K, Nesterenko PN, Paull B (2006) On-line preconcentration of pharmaceutical residues from large volume water samples using short reversed-phase monolithic cartridges coupled to LC-UV-ESI-MS. Talanta 70:1117–1128
López-Serna R, Pérez S, Ginebreda A, Petrović M, Barceló D (2010) Fully automated determination of 74 pharmaceuticals in environmental and waste waters by online solid phase extraction–liquid chromatography-electrospray–tandem mass spectrometry. Talanta 83:410–424
Quintana JB, Miro M, Estela JM, Cerdà V (2006) Automated on-line renewable solid-phase extraction-liquid chromatography exploiting multisyringe flow injection-bead injection lab-on-valve analysis. Anal Chem 78:2832–2840
Gros M, Petrović M, Barceló D (2006) Development of a multi-residue analytical methodology based on liquid chromatography–tandem mass spectrometry (LC–MS/MS) for screening and trace level determination of pharmaceuticals in surface and wastewaters. Talanta 70:678–690
Azzouz A, Ballesteros E (2012) Combined microwave-assisted extraction and continuous solid-phase extraction prior to gas chromatography–mass spectrometry determination of pharmaceuticals, personal care products and hormones in soils, sediments and sludge. Sci Total Environ 419:208–215
Snow DD, Damon-Powell T, Onanong S, Cassada DA (2013) Sensitive and simplified analysis of natural and synthetic steroids in water and solids using on-line solid-phase extraction and microwave-assisted solvent extraction coupled to liquid chromatography tandem mass spectrometry atmospheric pressure photoionization. Anal Bioanal Chem 405:1759–1771
Ternes TA, Andersen H, Gilberg D, Bonerz M (2002) Determination of estrogens in sludge and sediments by liquid extraction and GC/MS/MS. Anal Chem 74:3498–3504
Chenxi W, Spongberg AL, Witter JD (2008) Determination of the persistence of pharmaceuticals in biosolids using liquid-chromatography tandem mass spectrometry. Chemosphere 73:511–518
(2014) ameli.fr - Médicament. In: MEDICAM Database. http://www.ameli.fr/l-assurance-maladie/statistiques-et-publications/donnees-statistiques/medicament/medic-am-2008-2013.php. Accessed 9 Sep 2014
Gómez MJ, Petrović M, Fernández-Alba AR, Barceló D (2006) Determination of pharmaceuticals of various therapeutic classes by solid-phase extraction and liquid chromatography–tandem mass spectrometry analysis in hospital effluent wastewaters. J Chromatogr A 1114:224–233
Camel V (2000) Microwave-assisted solvent extraction of environmental samples. TrAC Trends Anal Chem 19:229–248
Madej K (2009) Microwave-assisted and cloud-point extraction in determination of drugs and other bioactive compounds. TrAC Trends Anal Chem 28:436–446
Sanchez-Prado L, Garcia-Jares C, Llompart M (2010) Microwave-assisted extraction: application to the determination of emerging pollutants in solid samples. J Chromatogr A 1217:2390–2414
Bielicka-Daszkiewicz K, Voelkel A (2009) Theoretical and experimental methods of determination of the breakthrough volume of SPE sorbents. Talanta 80:614–621
Baker DR, Kasprzyk-Hordern B (2011) Critical evaluation of methodology commonly used in sample collection, storage and preparation for the analysis of pharmaceuticals and illicit drugs in surface water and wastewater by solid phase extraction and liquid chromatography–mass spectrometry. J Chromatogr A 1218:8036–8059
Lee J, Jang E-S, Kim B (2013) Development of isotope dilution-liquid chromatography/mass spectrometry combined with standard addition techniques for the accurate determination of tocopherols in infant formula. Anal Chim Acta 787:132–139
Jelić A, Petrović M, Barceló D (2009) Multi-residue method for trace level determination of pharmaceuticals in solid samples using pressurized liquid extraction followed by liquid chromatography/quadrupole-linear ion trap mass spectrometry. Talanta 80:363–371
Barclay VKH, Tyrefors NL, Johansson IM, Pettersson CE (2012) Trace analysis of fluoxetine and its metabolite norfluoxetine. Part II: enantioselective quantification and studies of matrix effects in raw and treated wastewater by solid phase extraction and liquid chromatography–tandem mass spectrometry. J Chromatogr A 1227:105–114
Zhao X, Metcalfe CD (2008) Characterizing and compensating for matrix effects using atmospheric pressure chemical ionization liquid chromatography–tandem mass spectrometry: analysis of neutral pharmaceuticals in municipal wastewater. Anal Chem 80:2010–2017
Santos LHMLM, Gros M, Rodriguez-Mozaz S, Delerue-Matos C, Pena A, Barceló D, Montenegro MCBSM (2013) Contribution of hospital effluents to the load of pharmaceuticals in urban wastewaters: identification of ecologically relevant pharmaceuticals. Sci Total Environ 461–462:302–316
Prasse C, Schlüsener MP, Schulz R, Ternes TA (2010) Antiviral drugs in wastewater and surface waters: a new pharmaceutical class of environmental relevance? Environ Sci Technol 44:1728–1735
Baker DR, Kasprzyk-Hordern B (2013) Spatial and temporal occurrence of pharmaceuticals and illicit drugs in the aqueous environment and during wastewater treatment: new developments. Sci Total Environ 454–455:442–456
Huerta-Fontela M, Galceran MT, Ventura F (2010) Fast liquid chromatography–quadrupole-linear ion trap mass spectrometry for the analysis of pharmaceuticals and hormones in water resources. J Chromatogr A 1217:4212–4222, 007
Ashton D, Hilton M, Thomas KV (2004) Investigating the environmental transport of human pharmaceuticals to streams in the United Kingdom. Sci Total Environ 333:167–184
González Alonso S, Catalá M, Maroto RR, Gil JLR, de Miguel ÁG, Valcárcel Y (2010) Pollution by psychoactive pharmaceuticals in the rivers of Madrid metropolitan area (Spain). Environ Int 36:195–201
Vulliet E, Cren-Olivé C (2011) Screening of pharmaceuticals and hormones at the regional scale, in surface and groundwaters intended to human consumption. Environ Pollut 159:2929–2934
Bergen BJ, Nelson WG, Pruell RJ (1993) Partitioning of polychlorinated biphenyl congeners in the seawater of New Bedford Harbor, Massachusetts. Environ Sci Technol 27:938–942
Smith KEC, McLachlan MS (2006) Concentrations and partitioning of polychlorinated biphenyls in the surface waters of the southern Baltic Sea-seasonal effects. Environ Toxicol Chem 25:2569–2575
Ramil M, El Aref T, Fink G, Scheurer M, Ternes TA (2010) Fate of beta blockers in aquatic-sediment systems: sorption and biotransformation. Environ Sci Technol 44:962–970
Schaffer M, Börnick H, Nödler K, Licha T, Worch E (2012) Role of cation exchange processes on the sorption influenced transport of cationic β-blockers in aquifer sediments. Water Res 46:5472–5482
Sathyamoorthy S, Ramsburg CA (2013) Assessment of quantitative structural property relationships for prediction of pharmaceutical sorption during biological wastewater treatment. Chemosphere 92:639–646
Schultz MM, Furlong ET, Kolpin DW, Werner SL, Schoenfuss HL, Barber LB, Blazer VS, Norris DO, Vajda AM (2010) Antidepressant pharmaceuticals in two U.S. effluent-impacted streams: occurrence and fate in water and sediment, and selective uptake in fish neural tissue. Environ Sci Technol 44:1918–1925
Stewart M, Olsen G, Hickey CW, Ferreira B, Jelić A, Petrović M, Barcelo D (2014) A survey of emerging contaminants in the estuarine receiving environment around Auckland, New Zealand. Sci Total Environ 468–469:202–210
Acknowledgments
This study has been carried out in the framework of the Cluster of Excellence COTE. The authors would like to thank the Etiage program (Agence de l’Eau Adour-Garonne, the Communauté Urbaine de Bordeaux (CUB) and Lyonnaise des Eaux) and the Aquitaine Region and the European Union (CPER A2E project) for their financial support. Europe is moving in Aquitaine with the European Regional Development Fund.
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The authors declare that they have no competing interests.
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Aminot, Y., Litrico, X., Chambolle, M. et al. Development and application of a multi-residue method for the determination of 53 pharmaceuticals in water, sediment, and suspended solids using liquid chromatography-tandem mass spectrometry. Anal Bioanal Chem 407, 8585–8604 (2015). https://doi.org/10.1007/s00216-015-9017-3
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DOI: https://doi.org/10.1007/s00216-015-9017-3