Abstract
A fast and sensitive multianalyte/multiclass high-performance reversed-phase liquid chromatography–tandem mass spectrometry (LC–MS/MS) method was developed and validated for the simultaneous analysis of 89 pharmaceuticals in influent and effluent wastewater samples. The method developed consists of solid-phase extraction (SPE) using a hydrophilic–lipophilic-balanced polymer followed by LC–MS/MS with electrospray ionization in both positive mode and negative mode. The selected pharmaceuticals belong to different classes—analgesic/anti-inflammatory drugs, antibiotics, antiepileptics, β-adrenoceptor-blocking drugs, lipid-regulating agents, statins, and many others. The influence of the mobile phase composition on the sensitivity of the method, and the optimum conditions for SPE in terms of analyte recovery were extensively studied. Chromatographic separation was performed on an Atlantis T3 (100 mm × 2.1 mm, 3-μm) column with a gradient elution using methanol–0.01 % v/v formic acid as the mobile phase in positive ionization mode determination and methanol–acetonitrile–1 mM ammonium formate as the mobile phase in negative ionization mode determination. Recoveries for most of the compounds ranged from 50 to 120 %. Precision, expressed as relative standard deviations, was always below 15 %, and the method detection limits ranged from 1.06 ng/L (4-hydroxyomeprazole) to 211 ng/L (metformin). Finally, the method developed was applied to the determination of target analytes in wastewater samples obtained from the Psyttalia wastewater treatment plant, Athens, Greece. Although SPE of pharmaceuticals from wastewater samples and their determination by LC–MS/MS is a well-established technique, the uniqueness of this study lies in the simultaneous determination of a remarkable number of compounds belonging to more than 20 drug classes. Moreover, the LC–MS/MS method has been thoroughly optimized so that maximum sensitivity is achieved for most of the compounds, making the proposed method a valuable tool for pharmaceutical analysis in influent and effluent wastewater at the sub-nanogram per liter level.
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References
Dussault EB, Balakrishnan VK, Sverko E, Solomon KR, Sibley PK (2008) Environ Toxicol Chem 27:425–432
US Environmental Protection Agency (2010) Pharmaceuticals and personal care products (PPCPs). http://www.epa.gov/ppcp/basic2.html. Accessed 25 Feb 2015
Fent K, Weston AA, Caminada D (2006) Aquat Toxicol 76:122–159
Mompelat S, Le Bot B, Thomas O (2009) Environ Int 35:803–814
Buchberger WW (2011) J Chromatogr A 1218:603–618
Carlsson C, Johansson AK, Alvan G, Bergman K, Kühler T (2006) Sci Total Environ 364:67–87
Cleuvers M (2003) Toxicol Lett 142:185–194
Nödler K, Licha T, Bester K, Sauter M (2010) J Chromatogr A 1217:6511–6521
Gross M, Petrović M, Barceló D (2006) Talanta 70:678–690
Tarcomnicu I, van Nuijs ALN, Simons W, Bervoets L, Blust R, Jorens PG, Neels H, Covaci A (2011) Talanta 83:795–803
Gracia-Lor E, Sanchez JV, Hernandez F (2010) J Chromatogr A 1217:622–632
Huerta-Fontela M, Galceran MT, Ventura F (2010) J Chromatogr A 1217:4212–4222
Lopez-Serna R, Petrović M, Barceló D (2011) Chemosphere 85:1390–1399
Ferrer I, Zweigenbaum JA, Thurman EM (2010) J Chromatogr A 1217:5674–5686
Gros M, Rodríguez-Mozaz S, Barceló D (2012) J Chromatogr A 1248:104–121
Laven M, Alsberg T, Yu Y, Adolfsson-Erici J (2009) J Chromatogr A 1216:49–62
Madureira TV, Barreiro JC, Rocha MJ, Cass QB, Tiritan ME (2009) J Chromatogr A 1216:7033–7042
Rodil R, Quintana JB, Lopez-Mahia P, Muniategui-Lorenzo S, Prada- Rodriguez D (2009) J Chromatogr A 1216:2958–2969
Huntscha S, Singer HP, McArdell CS, Frank CE, Hollender J (2012) J Chromatogr A 1268:74–83
Boleda R, Galceran T, Ventura F (2013) J Chromatogr A 1286:146–158
Gilart N, Marcé RM, Borrull F, Fontanals N (2012) J Sep Sci 35:875–882
Gracia-Lor E, Martínez M, Sancho JV, Peñuela G, Hernández F (2012) Talanta 99:1011–1023
Ibanez M, Guerrero C, Sancho JV, Hernandez F (2009) J Chromatogr A 1216:2529–2539
Kim H, Hong Y, Park J, Sharma VK, Cho S (2013) Chemosphere 91:888–894
Dorival-García N, Zafra-Gómez A, Cantarero S, Navalón A, Vílchez JL (2013) Microchem J 106:323–333
Togola A, Budzinski H (2008) J Chromatogr A 1177:150–158
Guitart C, Readman JW (2010) Anal Chim Acta 658:32–40
Varga M, Dobor J, Helenkár A, Jurecska L, Yao J, Záray G (2010) Microchem J 95:353–358
Hu R, Yang Z, Zhang L (2011) Talanta 85:1751–1759
Unceta N, Sampedro MC, Abu Bakar NK, Gσmez-Caballero A, Goicolea MA, Barrio RJ (2010) J Chromatogr A 1217:3392–3399
Trenholm RA, Vanderford BJ, Snyder SA (2009) Talanta 79:1425–1432
Basheer C, Lee J, Pedersen-Bjergaard S, Rasmussen KE, Lee HK (2010) J Chromatogr A 1217:6661–6667
Gilart N, Miralles N, Marcé RM, Borrull F, Fontanals N (2013) Anal Chim Acta 774:51–60
Kim DH, Lee DW (2003) J Chromatogr A 984:153–158
Barbosa J, Toro I, Bergés R, Sanz-Nebot V (2001) J Chromatogr A 915:85–96
Rainville PD, Smith NW, Cowan D, Plumb RS (2012) J Pharm Biomed 59:138–150
Llorca M, Gros M, Rodríguez-Mozaz S, Barceló D (2014) J Chromatogr A 1369:43–51
Gros M, Petrovic M, Barcelo D (2009) Anal Chem 81:898–912
WADA Project Team (2003) WADA technical document – TD2003IDCR: identification criteria for qualitative assays. http://www.wada-ama.org/rtecontent/document/criteria_1_2.pdf
European Commission (2002) Off J Eur Commun L 221:8–36
Borecka M, Białk-Bielińska A, Siedlewicz G, Kornowska K, Kumirska J, Stepnowski P, Pazdro K (2013) J Chromatogr A 1304:138–146
Gómez-Pérez ML, Plaza-Bolaños P, Romero-González R, Martínez-Vidal JL, Garrido-Frenich A (2012) J Chromatogr A 1248:130–138
Ashcroft AE (1997) In: Barnett NW (ed) Organic mass spectrometry. Royal Society of Chemistry, Cambridge
Mutavdžić Pavlović D, Babić S, Dolar D, Ašperger D, Košutić K, Horvat AJM, Kaštelan-Macan M (2010) J Sep Sci 33:258–267
Zhang ZL, Zhou JL (2007) J Chromatogr A 1154:205–213
Νováková L, Šatínský D, Solich P (2008) Trends Anal Chem 27:352–367
Miao XS, Metcalfe CD (2003) J Chromatogr A 998:133–141
Wu J, Qian X, Yang Z, Zhang L (2010) J Chromatogr A 1217:1471–1475
Scheurer M, Michel A, Brauch HJ, Ruck W, Sacher F (2012) Water Res 46:4790–4802
Martín J, Buchberger W, Santos JL, Alonso E, Aparicio I (2012) J Chromatogr B 895–896:94–101
Kosma CI, Lambropoulou DA, Albanis TA (2015) Water Res 70:436–448
Reyes-Contreras C, Matamoros V, Ruiz I, Soto M, Bayona JM (2011) Chemosphere 84:1200–1207
Kasprzyk-Hordern B, Dinsdale RM, Guwy AJ (2008) Anal Bioanal Chem 391:1293–1308
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Published in the topical collection Advances in LC-MS/MS Analysis with guest editors Damià Barceló and Mira Petrovic
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Dasenaki, M.E., Thomaidis, N.S. Multianalyte method for the determination of pharmaceuticals in wastewater samples using solid-phase extraction and liquid chromatography–tandem mass spectrometry. Anal Bioanal Chem 407, 4229–4245 (2015). https://doi.org/10.1007/s00216-015-8654-x
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DOI: https://doi.org/10.1007/s00216-015-8654-x