Advertisement

Analytical and Bioanalytical Chemistry

, Volume 400, Issue 2, pp 587–594 | Cite as

Semi-automated liquid chromatography–mass spectrometry (LC–MS/MS) method for basic pesticides in wastewater effluents

  • Michael G. Cahill
  • Giovanni Caprioli
  • Mary Stack
  • Sauro Vittori
  • Kevin J. JamesEmail author
Original Paper

Abstract

Effluent from wastewater treatment plants have been identified as an important source of micro-organic contaminants in the environment. An online high-performance liquid chromatography–heated electrospray ionization tandem mass spectrometric method was developed and validated for the determination of basic pesticides in effluent wastewaters. Most available methods for pesticide analysis of wastewater samples are time-consuming, require complex clean-up steps and are difficult to automate. The method developed used a simple solid-phase extraction clean-up for salt and lipid reduction. On-line sample pre-concentration was performed using a reversed phase (C18) column, and analytes were separated by back-flushing onto an analytical column (C8) with detection using QqQ MS. An option to increase MS resolution was exploited to minimize interference from endogenous compounds in the matrix. A better than unit mass resolution was used (Q1 full width half maximum (FWHM) = 0.2 Da and Q3 FWHM = 0.7 Da), which was as rugged as a unit resolution method, and improved signal/noise and better detection limits were achieved for the targeted basic pesticides. This method was applied to the determination of 11 pesticides, including methoxytriazine, chlorotriazines, chloroacetanilides, phenylurea and carbamate pesticides. The percentage recovery values for these pesticides using the online trapping column were within the range, 73–95%, with relative standard deviation (RSD) values <8.9%. The highest concentrations of these pesticides in wastewater effluents in County Cork, Ireland, were simazine (0.51 μg/L), prometon (0.14 μg/L), diuron (0.21 μg/L) and atrazine (0.19 μg/L).

Online Abstract Figure

Effect of mass resolution change on signal/noise in the ion chromatograms for simazine at a) resolution setting, FWHM = 0.6 Da, b) resolution setting, FWHM = 0.2 Da.

Keywords

Priority pollutants Online solid-phase extraction Triple quadrupole mass analyzer 

Notes

Acknowledgements

This research was funded by the Environmental Protection Agency of Ireland, STRIVE program (2007–2013); Monitoring Criteria for Priority Chemicals Leading to Emission Factors, and the Higher Education Authority of Ireland, as part of the EU Structural Funds Programs (2007–2013) and the European Regional Development Fund; Program for Research in Third Level Institutions (PRTLI-4), Environment and Climate Change: Impacts and Responses.

References

  1. 1.
    Vryzas Z, Vassiliou G, Alexoudis C, Papadopoulou-Mourkidou E (2009) Water Res 43:1–10CrossRefGoogle Scholar
  2. 2.
    Burrows HD, Canle LM, Santaballa JA, Steenken S (2002) J Photochem Photobiol 67:71–108CrossRefGoogle Scholar
  3. 3.
    Dagnac T, Garcia-Chao M, Pulleiro P, Garcia-Jares C, Llompart M (2009) J Chromatogr A 1216:3702–3709CrossRefGoogle Scholar
  4. 4.
    Terzic S, Senta I, Ahel M, Gros M, Petrovic M, Barcelo D, Müller J, Knepper T, Martí I, Ventura F, Jovancic P, Jabucar D (2008) Sci Total Environ 399:66–77CrossRefGoogle Scholar
  5. 5.
    Alvarez DA, Stackelberg PE, Petty JD, Huckins JN, Furlong ET, Zaugg SD, Meyer MT (2005) Chemosphere 61:610–622CrossRefGoogle Scholar
  6. 6.
    Knepper TP (2002) J Chromatogr A 974:111–121CrossRefGoogle Scholar
  7. 7.
    Kuster M, López de Alda M, Barceló D (2009) J Chromatogr A 1216:520–529CrossRefGoogle Scholar
  8. 8.
    Rivas IP, Gil-Alegre ME, Torres-Suárez AI (2006) Anal Chim Acta 557:245–251CrossRefGoogle Scholar
  9. 9.
    Gómez MJ, Agüera A, Mezcua M, Hurtado J, Mocholí F, Fernández-Alba AR (2007) Talanta 73:314–320CrossRefGoogle Scholar
  10. 10.
    Ferrer I, Barber LB, Thurman EM (2009) J Chromatogr A 1216:6024–6032CrossRefGoogle Scholar
  11. 11.
    Song X, Budde WL (1998) J Chromatogr A 829:327–340CrossRefGoogle Scholar
  12. 12.
    Ferrer I, Thurman ME (2007) J Chromatogr A 1175:24–37CrossRefGoogle Scholar
  13. 13.
    Castiglioni S, Zuccato E, Chiabrando C, Fanelli R, Bagnati R (2008) Mass Spectrom Rev 27:378–394CrossRefGoogle Scholar
  14. 14.
    Ibáñez M, Guerrero C, Sancho JV, Hernández F (2009) J Chromatogr A 1216:2529–2539CrossRefGoogle Scholar
  15. 15.
    Soler C, Hamilton B, Furey A, James KJ, Mañes J, Picó Y (2007) Anal Chem 79:1492–1501CrossRefGoogle Scholar
  16. 16.
    Ibáñez M, Sancho JV, Hernández F, McMillan D, Rao R (2008) TrAC Trends Anal Chem 27:481–489CrossRefGoogle Scholar
  17. 17.
    Hogenboom AC, Niessen WMA, Brinkman UAT (1998) J Chromatogr A 794:201–210CrossRefGoogle Scholar
  18. 18.
    Cahill MG, Caprioli G, Vittori S, James KJ (2010) J Mass Spectrom 45:1019–1025CrossRefGoogle Scholar
  19. 19.
    Marín JM, Gracia-Lor E, Sancho JV, López FJ, Hernández F (2009) J Chromatogr A 1216:1410–1420CrossRefGoogle Scholar
  20. 20.
    Senta I, Terzić S, Ahel M (2008) Chromatographia 68:747–758CrossRefGoogle Scholar
  21. 21.
    Viglino L, Aboulfadi K, Mahvelat AD, Prevost M, Sauve S (2008) J Environ Monit 10:482–489CrossRefGoogle Scholar
  22. 22.
    Postigo C, de Alda M, Barceló D, Ginebreda A, Garrido T, Fraile J (2010) J Hydrol 383:83–92CrossRefGoogle Scholar
  23. 23.
    Pucci V, Di Palma S, Alfieri A, Bonelli F, Monteagudo E (2009) J Pharm Biomed Anal 50:867–871CrossRefGoogle Scholar
  24. 24.
    Ismaiel OA, Halquist MS, Elmamly MY, Shalaby A, Karnes HT (2008) J Chromatogr B 875:333–343CrossRefGoogle Scholar
  25. 25.
    Hernández F, Pozo ÓJ, Sancho JV, López FJ, Marín JM, Ibáñez M (2005) TrAC Trends Anal Chem 24:596–612CrossRefGoogle Scholar
  26. 26.
    Calderoli S, Colombo E, Frigerio E, James CA, Sibum M (2003) J Pharm Biomed Anal 32:601–607CrossRefGoogle Scholar
  27. 27.
    Jemal M, Ouyang Z (2003) Rapid Commun Mass Spectrom 17:24–38CrossRefGoogle Scholar
  28. 28.
    Kellmann M, Muenster H, Zomer P, Mol H (2009) J Am Soc Mass Spectrom 20:1464–1476CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Michael G. Cahill
    • 1
    • 2
  • Giovanni Caprioli
    • 3
  • Mary Stack
    • 2
  • Sauro Vittori
    • 3
  • Kevin J. James
    • 1
    • 2
    Email author
  1. 1.Environmental Research InstituteUniversity College CorkCorkIreland
  2. 2.PROTEOBIO (Mass Spectrometry Centre)Cork Institute of TechnologyCorkIreland
  3. 3.Dipartimento di Scienze Chimiche, Facoltà di FarmaciaUniversità di CamerinoCamerinoItaly

Personalised recommendations