Skip to main content
SpringerLink
Log in

Eco-friendly LC–MS/MS method for analysis of multi-class micropollutants in tap, fountain, and well water from northern Portugal

  • Research Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

Organic micropollutants present in drinking water (DW) may cause adverse effects for public health, and so reliable analytical methods are required to detect these pollutants at trace levels in DW. This work describes the first green analytical methodology for multi-class determination of 21 pollutants in DW: seven pesticides, an industrial compound, 12 pharmaceuticals, and a metabolite (some included in Directive 2013/39/EU or Decision 2015/495/EU). A solid-phase extraction procedure followed by ultra-high-performance liquid chromatography coupled to tandem mass spectrometry (offline SPE–UHPLC–MS/MS) method was optimized using eco-friendly solvents, achieving detection limits below 0.20 ng L−1. The validated analytical method was successfully applied to DW samples from different sources (tap, fountain, and well waters) from different locations in the north of Portugal, as well as before and after bench-scale UV and ozonation experiments in spiked tap water samples. Thirteen compounds were detected, many of them not regulated yet, in the following order of frequency: diclofenac > norfluoxetine > atrazine > simazine > warfarin > metoprolol > alachlor > chlorfenvinphos > trimethoprim > clarithromycin ≈ carbamazepine ≈ PFOS > citalopram. Hazard quotients were also estimated for the quantified substances and suggested no adverse effects to humans.

Occurrence and removal of multi-class micropollutants in drinking water, analyzed by an eco-friendly LC–MS/MS method

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  1. Benitez FJ, García J, Acero JL, Real FJ, Roldan G. Non-catalytic and catalytic wet air oxidation of pharmaceuticals in ultra-pure and natural waters. Process Saf Environ Prot. 2011;89(5):334–41.

    Article  CAS  Google Scholar 

  2. Lin T, Yu S, Chen W. Occurrence, removal and risk assessment of pharmaceutical and personal care products (PPCPs) in an advanced drinking water treatment plant (ADWTP) around Taihu Lake in China. Chemosphere. 2016;152:1–9.

    Article  CAS  Google Scholar 

  3. Kidd KA, Blanchfield PJ, Mills KH, Palace VP, Evans RE, Lazorchak JM, et al. Collapse of a fish population after exposure to a synthetic estrogen. Proc Natl Acad Sci U S A. 2007;104(21):8897–901.

    Article  CAS  Google Scholar 

  4. Santos LH, Araujo AN, Fachini A, Pena A, Delerue-Matos C, Montenegro MC. Ecotoxicological aspects related to the presence of pharmaceuticals in the aquatic environment. J Hazard Mater. 2010;175(1-3):45–95.

    Article  CAS  Google Scholar 

  5. Directive_98/83/EC. Council Directive 98/83/EC of 3 November 1998 on the quality of water intended for human consumption. Off J Eur Commun. 1998;330:32–54.

    Google Scholar 

  6. Directive_2006/118/EC. Directive 2006/118/EC of the European Parliament and of the Council of 12 December 2006 on the protection of groundwater against pollution and deterioration. Off J Eur Union. 2006;372:1–31.

    Google Scholar 

  7. Directive. 2000/60/EC of the European Parliament and of the Council of 23 October 2000 establishing a framework for Community action in the field of water policy. Off J Eur Commun. 2000;L327:1–72.

  8. Directive. 2008/105/EC of the European Parliament and of the Council of 16 December 2008 on environmental quality standards in the field of water policy, amending and subsequently repealing Council Directives 82/176/EEC, 83/513/EEC, 84/156/EEC, 84/491/EEC, 86/280/EEC and amending Directive 2000/60/EC of the European Parliament and of the Council. Off J Eur Union. 2008;L348:84–97.

  9. Directive_39. Directive 2013/39/EU of the European Parliament and of the Council of 12 August 2013 amending Directives 2000/60/EC and 2008/105/EC as regards priority substances in the field of water policy. Off J Eur Union. 2013;L226:1–17.

  10. Decision_495. Commission Implementing Decision (EU) 2015/495 of 20 March 2015 establishing a watch list of substances for Union-wide monitoring in the field of water policy pursuant to Directive 2008/105/EC of the European Parliament and of the Council. Off J Eur Union. 2015;L78:40–2.

  11. Barbosa MO, Moreira NFF, Ribeiro AR, Pereira MFR, Silva AMT. Occurrence and removal of organic micropollutants: an overview of the watch list of EU Decision 2015/495. Water Res. 2016;94:257–79.

    Article  CAS  Google Scholar 

  12. Dasenaki ME, Thomaidis NS. Multianalyte method for the determination of pharmaceuticals in wastewater samples using solid-phase extraction and liquid chromatography-tandem mass spectrometry. Anal Bioanal Chem. 2015;407(15):4229–45.

    Article  CAS  Google Scholar 

  13. Gago-Ferrero P, Borova V, Dasenaki ME, Thomaidis NS. Simultaneous determination of 148 pharmaceuticals and illicit drugs in sewage sludge based on ultrasound-assisted extraction and liquid chromatography-tandem mass spectrometry. Anal Bioanal Chem. 2015;407(15):4287–97.

    Article  CAS  Google Scholar 

  14. Ferrer I, Zweigenbaum JA, Thurman EM. Analysis of 70 Environmental Protection Agency priority pharmaceuticals in water by EPA Method 1694. J Chromatogr A. 2010;1217(36):5674–86.

    Article  CAS  Google Scholar 

  15. Maldaner L, Jardim IC. Determination of some organic contaminants in water samples by solid-phase extraction and liquid chromatography-tandem mass spectrometry. Talanta. 2012;100:38–44.

    Article  CAS  Google Scholar 

  16. Rodil R, Quintana JB, Lopez-Mahia P, Muniategui-Lorenzo S, Prada-Rodriguez D. Multi-residue analytical method for the determination of emerging pollutants in water by solid-phase extraction and liquid chromatography-tandem mass spectrometry. J Chromatogr A. 2009;1216(14):2958–69.

    Article  CAS  Google Scholar 

  17. Kowal S, Balsaa P, Werres F, Schmidt TC. Fully automated standard addition method for the quantification of 29 polar pesticide metabolites in different water bodies using LC-MS/MS. Anal Bioanal Chem. 2013;405(19):6337–51.

    Article  CAS  Google Scholar 

  18. Mann O, Pock E, Wruss K, Wruss W, Krska R. Development and validation of a fully automated online-SPE–ESI–LC–MS/MS multi-residue method for the determination of different classes of pesticides in drinking, ground and surface water. Int J Environ Anal Chem. 2016;96(4):353–72.

    Article  CAS  Google Scholar 

  19. Sancho JV, Pozo OJ, Hernandez F. Liquid chromatography and tandem mass spectrometry: a powerful approach for the sensitive and rapid multiclass determination of pesticides and transformation products in water. Analyst. 2004;129(1):38–44.

    Article  CAS  Google Scholar 

  20. Gros M, Rodriguez-Mozaz S, Barcelo D. Fast and comprehensive multi-residue analysis of a broad range of human and veterinary pharmaceuticals and some of their metabolites in surface and treated waters by ultra-high-performance liquid chromatography coupled to quadrupole-linear ion trap tandem mass spectrometry. J Chromatogr A. 2012;1248:104–21.

    Article  CAS  Google Scholar 

  21. Stolker AA, Niesing W, Hogendoorn EA, Versteegh JF, Fuchs R, Brinkman UA. Liquid chromatography with triple-quadrupole or quadrupole-time of flight mass spectrometry for screening and confirmation of residues of pharmaceuticals in water. Anal Bioanal Chem. 2004;378(4):955–63.

    Article  CAS  Google Scholar 

  22. Wang C, Shi H, Adams CD, Gamagedara S, Stayton I, Timmons T, et al. Investigation of pharmaceuticals in Missouri natural and drinking water using high performance liquid chromatography-tandem mass spectrometry. Water Res. 2011;45(4):1818–28.

    Article  CAS  Google Scholar 

  23. de Jesus Gaffney V, Almeida CM, Rodrigues A, Ferreira E, Benoliel MJ, Cardoso VV. Occurrence of pharmaceuticals in a water supply system and related human health risk assessment. Water Res. 2015;72:199–208.

    Article  Google Scholar 

  24. Cimetiere N, Soutrel I, Lemasle M, Laplanche A, Crocq A. Standard addition method for the determination of pharmaceutical residues in drinking water by SPE–LC–MS/MS. Environ Technol. 2013;34(22):3031–41.

    Article  CAS  Google Scholar 

  25. Idder S, Ley L, Mazellier P, Budzinski H. Quantitative on-line preconcentration-liquid chromatography coupled with tandem mass spectrometry method for the determination of pharmaceutical compounds in water. Anal Chim Acta. 2013;805:107–15.

    Article  CAS  Google Scholar 

  26. Boleda MR, Galceran MT, Ventura F. Validation and uncertainty estimation of a multiresidue method for pharmaceuticals in surface and treated waters by liquid chromatography-tandem mass spectrometry. J Chromatogr A. 2013;1286:146–58.

    Article  CAS  Google Scholar 

  27. Pinhancos R, Maass S, Ramanathan DM. High-resolution mass spectrometry method for the detection, characterization and quantitation of pharmaceuticals in water. J Mass Spectrom. 2011;46(11):1175–81.

    Article  CAS  Google Scholar 

  28. de la Guardia M, Garrigues S. The social responsibility of environmental analysis. TrEAC Trends Environ Anal Chem. 2014;3–4:7–13.

    Article  Google Scholar 

  29. Gałuszka A, Migaszewski Z, Namieśnik J. The 12 principles of green analytical chemistry and the SIGNIFICANCE mnemonic of green analytical practices. TrAC Trends Anal Chem. 2013;50:78–84.

    Article  Google Scholar 

  30. Shaaban H, Gorecki T. Current trends in green liquid chromatography for the analysis of pharmaceutically active compounds in the environmental water compartments. Talanta. 2015;132:739–52.

    Article  CAS  Google Scholar 

  31. Farré M, Pérez S, Gonçalves C, Alpendurada MF, Barceló D. Green analytical chemistry in the determination of organic pollutants in the aquatic environment. TrAC Trends Anal Chem. 2010;29(11):1347–62.

    Article  Google Scholar 

  32. Pena-Pereira F, Kloskowski A, Namieśnik J. Perspectives on the replacement of harmful organic solvents in analytical methodologies: a framework toward the implementation of a generation of eco-friendly alternatives. Green Chem. 2015;17(7):3687–705.

    Article  CAS  Google Scholar 

  33. Shaaban H. New insights into liquid chromatography for more eco-friendly analysis of pharmaceuticals. Anal Bioanal Chem. 2016. doi:10.1007/s00216-016-9726-2.

    Google Scholar 

  34. Schriks M, Heringa MB, van der Kooi MME, de Voogt P, van Wezel AP. Toxicological relevance of emerging contaminants for drinking water quality. Water Res. 2010;44(2):461–76.

    Article  CAS  Google Scholar 

  35. Mendoza A, Rodríguez-Gil JL, González-Alonso S, Mastroianni N, López de Alda M, Barceló D, et al. Drugs of abuse and benzodiazepines in the Madrid Region (Central Spain): seasonal variation in river waters, occurrence in tap water and potential environmental and human risk. Environ Int. 2014;70:76–87.

    Article  CAS  Google Scholar 

  36. Bruce GM, Pleus RC, Snyder SA. Toxicological relevance of pharmaceuticals in drinking water. Environ Sci Technol. 2010;44(14):5619–26.

    Article  CAS  Google Scholar 

  37. Houtman CJ, Kroesbergen J, Lekkerkerker-Teunissen K, van der Hoek JP. Human health risk assessment of the mixture of pharmaceuticals in Dutch drinking water and its sources based on frequent monitoring data. Sci Total Environ. 2014;496:54–62.

    Article  CAS  Google Scholar 

  38. Ribeiro AR, Pedrosa M, Moreira NFF, Pereira MFR, Silva AMT. Environmental friendly method for urban wastewater monitoring of micropollutants defined in the Directive 2013/39/EU and Decision 2015/495/EU. J Chromatogr A. 2015;1418:140–9.

    Article  CAS  Google Scholar 

  39. ICH. Validation of analytical procedures: text and methodology Q2(R1). International Conference on Harmonization. 1996;1–13.

  40. Ribeiro AR, Maia AS, Moreira IS, Afonso CM, Castro PML, Tiritan ME. Enantioselective quantification of fluoxetine and norfluoxetine by HPLC in wastewater effluents. Chemosphere. 2014;95:589–96.

    Article  CAS  Google Scholar 

  41. Ribeiro AR, Santos LHMLM, Maia AS, Delerue-Matos C, Castro PML, Tiritan ME. Enantiomeric fraction evaluation of pharmaceuticals in environmental matrices by liquid chromatography-tandem mass spectrometry. J Chromatogr A. 2014;1363:226–35.

    Article  CAS  Google Scholar 

  42. US Food and Drug Administration. Bioanalytical method validation: guidance for industry. 2001. http://www.fda.gov/downloads/Drugs/GuidanceComplianceRegulatoryInformation/Guidances/ucm070107.pdf. Accessed Mar 2013.

  43. Madureira TV, Barreiro JC, Rocha MJ, Cass QB, Tiritan ME. Pharmaceutical trace analysis in aqueous environmental matrices by liquid chromatography-ion trap tandem mass spectrometry. J Chromatogr A. 2009;1216(42):7033–42.

    Article  CAS  Google Scholar 

  44. Moreira NF, Orge CA, Ribeiro AR, Faria JL, Nunes OC, Pereira MF, et al. Fast mineralization and detoxification of amoxicillin and diclofenac by photocatalytic ozonation and application to an urban wastewater. Water Res. 2015;87:87–96.

    Article  CAS  Google Scholar 

  45. Schwab BW, Hayes EP, Fiori JM, Mastrocco FJ, Roden NM, Cragin D, et al. Human pharmaceuticals in US surface waters: a human health risk assessment. Regul Toxicol Pharm. 2005;42(3):296–312.

    Article  CAS  Google Scholar 

  46. Australian Governement. ADI LIST - acceptable daily intakes for agricultural and veterinary chemicals. 2015. Commonwealth of Australia, Canberra, Australia.

  47. Bielicka-Daszkiewicz K, Voelkel A. Theoretical and experimental methods of determination of the breakthrough volume of SPE sorbents. Talanta. 2009;80(2):614–21.

    Article  CAS  Google Scholar 

  48. López-Serna R, Petrović M, Barceló D. Development of a fast instrumental method for the analysis of pharmaceuticals in environmental and wastewaters based on ultra high performance liquid chromatography (UHPLC)–tandem mass spectrometry (MS/MS). Chemosphere. 2011;85(8):1390–9.

    Article  Google Scholar 

  49. Cotton J, Leroux F, Broudin S, Poirel M, Corman B, Junot C, et al. Development and validation of a multiresidue method for the analysis of more than 500 pesticides and drugs in water based on on-line and liquid chromatography coupled to high resolution mass spectrometry. Water Res. 2016;104:20–7.

    Article  CAS  Google Scholar 

  50. Maia AS, Ribeiro AR, Amorim CL, Barreiro JC, Cass QB, Castro PML, et al. Degradation of fluoroquinolone antibiotics and identification of metabolites/transformation products by liquid chromatography–tandem mass spectrometry. J Chromatogr A. 2014;1333:87–98.

    Article  CAS  Google Scholar 

  51. K’Oreje KO, Vergeynst L, Ombaka D, De Wispelaere P, Okoth M, Van Langenhove H, et al. Occurrence patterns of pharmaceutical residues in wastewater, surface water and groundwater of Nairobi and Kisumu city, Kenya. Chemosphere. 2016;149:238–44.

    Article  Google Scholar 

Download references

Acknowledgments

Financial support for this work was provided by project NORTE-07-0202-FEDER-038900 (NEPCAT), financed by Fundo Europeu de Desenvolvimento Regional (FEDER) through ON2 (Programa Operacional do Norte) and Quadro de Referência Estratégica Nacional (QREN). This work was co-financed by QREN, ON2 and FEDER, under Programme COMPETE (Projects NORTE-07-0124-FEDER-000015 and NORTE-07-0162-FEDER-000050) and by Fundação para a Ciência e a Tecnologia (FCT) and FEDER through COMPETE 2020 (Project UID/EQU/50020/2013 - POCI-01-0145-FEDER-006984). MOB acknowledges the research grant from project “AIProcMat@N2020 - Advanced Industrial Processes and Materials for a Sustainable Northern Region of Portugal 2020”, with the reference NORTE-01-0145-FEDER-000006, supported by Norte Portugal Regional Operational Programme (NORTE 2020), under the Portugal 2020 Partnership Agreement, through the European Regional Development Fund (ERDF) and of Project POCI-01-0145-FEDER-006984 – Associate Laboratory LSRE-LCM funded by ERDF throug COMPETE2020 - Programa Operacional Competitividade e Internacionalização (POCI) – and by national funds through FCT. ARR and AMTS acknowledge respectively the research grant from FCT (Ref. SFRH/BPD/101703/2014) and the FCT Investigator 2013 Programme (IF/01501/2013), with financing from the European Social Fund and the Human Potential Operational Programme.

Author information

Authors and Affiliations

  1. Laboratory of Separation and Reaction Engineering - Laboratory of Catalysis and Materials (LSRE-LCM), Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465, Porto, Portugal

    Marta O. Barbosa, Ana R. Ribeiro, Manuel F. R. Pereira & Adrián M. T. Silva

Authors
  1. Marta O. Barbosa
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ana R. Ribeiro
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Manuel F. R. Pereira
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Adrián M. T. Silva
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Ana R. Ribeiro.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(PDF 1.10 mb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Barbosa, M.O., Ribeiro, A.R., Pereira, M.F.R. et al. Eco-friendly LC–MS/MS method for analysis of multi-class micropollutants in tap, fountain, and well water from northern Portugal. Anal Bioanal Chem 408, 8355–8367 (2016). https://doi.org/10.1007/s00216-016-9952-7

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-016-9952-7

Keywords

Search

Navigation