Screening of pharmaceuticals and illicit drugs in wastewater and surface waters of Spain and Italy by high resolution mass spectrometry using UHPLC-QTOF MS and LC-LTQ-Orbitrap MS
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The existence of pharmaceuticals and illicit drugs (PIDs) in environmental waters has led many analytical chemists to develop screening methods for monitoring purposes. Water samples can contain a huge number of possible contaminants, commonly at low concentrations, which makes their detection and identification problematic. Liquid chromatography coupled with high resolution mass spectrometry (LC-HRMS) has proven itself effective in the screening of environmental contaminants. The present work investigates the use of the most popular HRMS instruments, quadrupole time-of-flight and linear trap quadrupole-Orbitrap, from two different laboratories. A suspect screening for PIDs was carried out on wastewater (influent and effluent) and surface water samples from Castellón, Eastern Spain, and Cremona, Northern Italy, incorporating a database of 107 PIDs (including 220 fragment ions). A comparison between the findings of both instruments and of the samples was made which highlights the advantages and drawbacks of the strategies applied in each case. In total, 28 compounds were detected and/or identified by either/both instruments with irbesartan, valsartan, benzoylecgonine and caffeine being the most commonly found compounds across all samples.
KeywordsLiquid chromatography Screening Pharmaceuticals Illicit drugs High resolution mass spectrometry
R. Bade, N. I. Rousis and E. Gracia-Lor acknowledge the European Union’s International Training Network SEWPROF (Marie Curie-FP7-PEOPLE Grant no. 317205) for their Early Stage Researcher (R. Bade and N. I. Rousis) and Experienced Researcher (E. Gracia-Lor) contracts. The financial support from the Spanish Ministry of Economy and Competitiveness (Ref CTQ2012-36189) and Generalitat Valenciana, Spain (research group of excellence PROMETEO II/2014/023; ISIC 2012/016) is also acknowledged.
We would like to thank Thermo Scientific who provided the software TraceFinder and particularly Claudia Martins for technical support.
Conflict of interest
The authors declare that they have no competing interests.
- 4.Brozinski J, Lahti M, Meierjohann A, Oikari A, Kronberg L (2013) The anti-inflammatory drugs diclofenac, naproxen and ibuprofen are found in the bile of wild fish caught downstream of a wastewater treatment plant. Environ Sci Technol 47:342–348. doi: 10.1021/es303013j
- 12.Hernández F, Bijlsma L, Sancho JV, Díaz R, Ibáñez M (2011) Rapid wide-scope screening of drugs of abuse, prescription drugs with potential for abuse and their metabolites in influent and effluent urban wastewater by ultrahigh pressure liquid chromatography-quadrupole-time-of-flight-mass spectrometry. Anal Chim Acta 684:87–97. doi: 10.1016/j.aca.2010.10.043 CrossRefGoogle Scholar
- 13.de Voogt P, Emke E, Helmus R, Panteliadis P, van Leerdam JA (2011) Determination of illicit drugs in the water cycle by LC-Orbtitrap MS. In: Castiglioni S, Zuccato E, Fanelli R (eds.) Illicit drugs environ. Occur. Anal. Fate Using Mass Spectrom., John Wiley & Sons, Ltd., pp. 87–114Google Scholar
- 14.Gómez MJ, Gómez-Ramos MM, Malato O, Mezcua M, Férnandez-Alba AR (2010) Rapid automated screening, identification and quantification of organic micro-contaminants and their main transformation products in wastewater and river waters using liquid chromatography-quadrupole-time-of-flight mass spectrometry with an accurate-mass. J Chromatogr A 1217:7038–7054. doi: 10.1016/j.chroma.2010.08.070 CrossRefGoogle Scholar
- 15.Gonzalez-Mariño I, Quintana JB, Rodriguez I, Gonzalez-Diez M, Cela R (2012) Screening and selective quantification of illicit drugs in wastewater by mixed-mode solid-phase extraction and quadrupole-time-of-flight liquid chromatography–mass spectrometry. Anal Chem 84:1708–1717. doi: 10.1021/ac202989e CrossRefGoogle Scholar
- 16.Ibáñez M, Guerrero C, Sancho JV, Hernández F (2009) Screening of antibiotics in surface and wastewater samples by ultra-high-pressure liquid chromatography coupled to hybrid quadrupole time-of-flight mass spectrometry. J Chromatogr A 1216:2529–2539. doi: 10.1016/j.chroma.2009.01.073 CrossRefGoogle Scholar
- 18.Wille K, Claessens M, Rappé K, Monteyne E, Janssen CR, De Brabander HF et al (2011) Rapid quantification of pharmaceuticals and pesticides in passive samplers using ultra high performance liquid chromatography coupled to high resolution mass spectrometry. J Chromatogr A 1218:9162–9173. doi: 10.1016/j.chroma.2011.10.039 CrossRefGoogle Scholar
- 20.SEWPROF ITN: a new paradigm in drug use and human health risk assessment: sewage profiling at the community level, (n.d.). http://sewprof-itn.eu/. Accessed 1 June 2015
- 23.Díaz R, Ibáñez M, Sancho JV, Hernández F (2011) Building an empirical mass spectra library for screening of organic pollutants by ultra-high-pressure liquid chromatography/hybrid quadrupole time-of-flight mass spectrometry. Rapid Commun Mass Spectrom 25:355–369. doi: 10.1002/rcm.4860 CrossRefGoogle Scholar
- 28.Gracia-Lor E, Sancho JV, Hernandez F (2011) Multi-class determination of around 50 pharmaceuticals, including 26 antibiotics, in environmental and wastewater samples by ultra-high performance liquid chromatography-tandem mass spectrometry. J Chromatogr A 1218:2264–2275. doi: 10.1016/j.chroma.2011.02.026 CrossRefGoogle Scholar
- 31.Al Aukidy M, Verlicchi P, Jelic A, Petrovic M, Barcelò D (2012) Monitoring release of pharmaceutical compounds: occurrence and environmental risk assessment of two WWTP effluents and their receiving bodies in the Po Valley, Italy. Sci Total Environ 438:15–25. doi: 10.1016/j.scitotenv.2012.08.061 CrossRefGoogle Scholar
- 33.Metamizolo: una lunga storia tra luci ed ombre. Accessed November 2014 http://www.farmacovigilanza.org/focus/200608/
- 34.N. 2/2006 Prescription data: IT del Sistema Nacional de Salud Volumen 30, Subgrupos ATC y Principios activos de mayor consumo en el Sistema Nacional de Salud en 2005, (2006) 42–49Google Scholar
- 35.A.I. del Farmaco, L’uso dei Farmaci in Italia (2013) http://www.agenziafarmaco.gov.it/sites/default/files/Rapporto_OsMED_2013.pdf
- 38.Kasprzyk-Hordern B, Dinsdale RM, Guwy AJ (2007) Multi-residue method for the determination of basic/neutral pharmaceuticals and illicit drugs in surface water by solid-phase extraction and ultra performance liquid chromatography-positive electrospray ionisation tandem mass spectrometry. J Chromatogr A 1161:132–145. doi: 10.1016/j.chroma.2007.05.074 CrossRefGoogle Scholar
- 39.Guidance document on analytical quality control and validation procedures for pesticides residues in food and feed, SANCO /12571/2013 (2013) http://ec.europa.eu/food/plant/pesticides/guidance_documents/docs/qualcontrol_en.pdf