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Determination of pesticides in sewage sludge from an agro-food industry using QuEChERS extraction followed by analysis with liquid chromatography-tandem mass spectrometry

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Abstract

An analytical method was developed and validated for the determination of ten pesticides in sewage sludge coming from an agro-food industry. The method was based on the application of Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) extraction for solid sewage sludge and SPE extraction for sludge aqueous phase, followed by liquid chromatography (LC) coupled to hybrid quadrupole/linear ion trap mass spectrometry (QqLIT-MS). The QuEChERS method was reported 14 years ago and nowadays is mainly applied to the analysis of pesticides in food. More recent applications have been reported in other matrices as sewage sludge, but the complexity of the matrix makes necessary the optimization of the cleanup step to improve the efficiency of the analysis. With this aim, several dispersive solid-phase extraction cleanup sorbents were tested, choosing C18 + PSA as a d-SPE sorbent. The proposed method was satisfactorily validated for most compounds investigated, showing recoveries higher than 80% in most cases, with the only exception of prochloraz (71%) at low concentration level. Limits of quantification were lower than 40 ng l−1 in the aqueous phase and below 40 ng g−1 in the solid phase for the majority of the analytes. The method was applied to solid sludge and the sludge aqueous phase coming from an agro-food industry which processes fruits and vegetables.

Application of LC/MS/MS advanced analytical techniques for determination of pesticides contained in sewage sludge

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References

  1. Köck-Schulmeyer M, Villagrasa M, López de Alda M, Céspedes-Sánchez R, Ventura F, Barceló D. Occurrence and behavior of pesticides in wastewater treatment plants and their environmental impact. Sci Total Environ. 2013;458–460:466–76.

    Article  Google Scholar 

  2. Masiá A, Vásquez K, Campo J, Picó Y. Assessment of two extraction methods to determine pesticides in soils, sediments and sludges. Application to the Túria River basin. J Chromatogr A. 2015;1378:19–31.

    Article  Google Scholar 

  3. Olofsson U, Brorström-Lundén E, Kylin H, Haglund P. Comprehensive mass flow analysis of Swedish sludge contaminants. Chemosphere. 2013;90(1):28–35.

    Article  CAS  Google Scholar 

  4. Karas P, Metsoviti A, Zisis V, Ehaliotis C, Omirou M, Papadopoulou ES, et al. Dissipation, metabolism and sorption of pesticides used in fruit-packaging plants: towards an optimized depuration of their pesticide-contaminated agro-industrial effluents. Sci Total Environ. 2015;530:129–39.

    Article  Google Scholar 

  5. Sánchez Pérez JA, Carra I, Sirtori C, Agüera A, Esteban B. Fate of thiabendazole through the treatment of a simulated agro-food industrial effluent by combined MBR/Fenton processes at μg/l scale. Water Res. 2014;51:55–63.

    Article  Google Scholar 

  6. Rivas G, Casas López JL, Esteban B, Sánchez Pérez JA. Controlling pH in biological depuration of industrial wastewater to enable micropollutant removal using a further advanced oxidation process. J Chem Technol Biotechnol. 2014;89:1274–82.

    Article  Google Scholar 

  7. Jiménez M, Maldonado MI, Rodríguez EM, Hernández-Ramírez A, Saggioro E, Carra I, et al. Supported TiO2 solar photocatalysis at semi-pilot scale: degradation of pesticides found in citrus processing industry wastewater, reactivity and influence of photogenerated species. J Chem Technol Biotechnol. 2015;90:149–57.

    Article  Google Scholar 

  8. Agüera A, Sirtori C, Esteban B, Cabrera A, Carra I, Sánchez Pérez JA (2013) Identification of biorecalcitrant micropollutants in food industry. Removal alternatives and characterization of generated transformation products, proc. Micropol & Ecohazard Zurich, Abstract IWA–11603.

  9. Tadeo JL, Sánchez-Brunete C, Albero B, García-Valcárcel AI. Determination of pesticide residues in sewage sludge: a review. J AOAC Int. 2010;93:1692–702.

    CAS  Google Scholar 

  10. European Committee for Standardization, Lebensmittel P, Aliments Q (2008) CEN15662:2008 Foods of plant origin—determination of pesticide residues using GC-MS and/or LC-MS/MS following acetonitrile extraction/partitioning and cleanup by dispersive SPE—QuEChERS-method. 24:1–83.

  11. Bruzzoniti MC, Checchini L, De Carlo RM, Orlandini S, Rivoira L, Del Bubba M. QuEChERS sample preparation for the determination of pesticides and other organic residues in environmental matrices: a critical review. Anal Bioanal Chem. 2014;406:4089–116.

    Article  CAS  Google Scholar 

  12. Peysson W, Vulliet E. Determination of 136 pharmaceuticals and hormones in sewage sludge using quick, easy, cheap, effective, rugged and safe extraction followed by analysis with liquid chromatography-time-of-flight-mass spectrometry. J Chromatogr A. 2013;1290:46–61.

    Article  CAS  Google Scholar 

  13. Ferhi S, Bourdat-Deschamps M, Daudin J-J, Houot S, Nélieu S. Factors influencing the extraction of pharmaceuticals from sewage sludge and soil: an experimental design approach. Anal Bioanal Chem. 2016;408:6153–68.

    Article  CAS  Google Scholar 

  14. Bourdat-Deschamps M, Leang S, Bernet N, Daudin J-J, Nélieu S. Multi-residue analysis of pharmaceuticals in aqueous environmental samples by online solid-phase extraction-ultra-high-performance liquid chromatography-tandem mass spectrometry: optimisation and matrix effects reduction by quick, easy, cheap, effective. J Chromatogr A. 2014;1349:11–23.

    Article  CAS  Google Scholar 

  15. Rossini D, Ciofi L, Ancillotti C, Checchini L, Bruzzoniti MC, Rivoira L, et al. Innovative combination of QuEChERS extraction with on-line solid-phase extract purification and pre-concentration, followed by liquid chromatography-tandem mass spectrometry for the determination of non-steroidal anti-inflammatory drugs and their metaboli. Anal Chim Acta. 2016;935:269–81.

    Article  CAS  Google Scholar 

  16. Schenck FJ, Hobbs JE. Evaluation of the quick, easy, cheap, effective, rugged, and safe (QuEChERS) approach to pesticide residue analysis. Bull Environ Contam Toxicol. 2004;73(1):24–30.

    Article  CAS  Google Scholar 

  17. Wang L, Huang X, Wang D, Chen Y, Xu D, Zhou Y. Determination of 32 sulfonylurea herbicide residues in sweet corns and green soybeans by QuEChERS-liquid chromatography-tandem mass spectrometry. Se Pu. 2015;33:501–7.

    CAS  Google Scholar 

  18. Nieto-García AJ, Romero-González R, GarridoFrenich A. Multi-pesticide residue analysis in nutraceuticals from grape seed extracts by gas chromatography coupled to triple quadrupole mass spectrometry. Food Control. 2015;47:369–80.

    Article  Google Scholar 

  19. Morris BD, Schriner RB. Development of an automated column solid-phase extraction cleanup of QuEChERS extracts, using a zirconia-based sorbent, for pesticide residue analyses by LC-MS/MS. J Agric Food Chem. 2015;63(21):5107–19.

    Article  CAS  Google Scholar 

  20. Li Y, Kelley RA, Anderson TD, Lydy MJ. Development and comparison of two multi-residue methods for the analysis of select pesticides in honey bees, pollen, and wax by gas chromatography-quadrupole mass spectrometry. Talanta. 2015;140:81–7.

    Article  CAS  Google Scholar 

  21. Melero JA, Sánchez-Vázquez R, Vasiliadou IA, MartínezCastillejo F, Bautista LF, Iglesias J, et al. Municipal sewage sludge to biodiesel by simultaneous extraction and conversion of lipids. Energy Convers Manag. 2015;103:111–8.

    Article  CAS  Google Scholar 

  22. Rivas G, Esteban B, Ponce-Robles L, Casas López JL, Agüera A, Sánchez Pérez JA. Fate of micropollutants during sewage sludge disintegration by low-frequency ultrasound. Chem Eng J. 2015;280:575–87.

    Article  Google Scholar 

  23. Ortega-Gómez E, Esteban B, Ballesteros Martín MM, Fernández Ibáñez P, Sánchez Pérez JA. Inactivation of natural enteric bacteria in real municipal wastewater by solar photo-Fenton at neutral pH. Water Res. 2014;63:316–24.

    Article  Google Scholar 

  24. Anastassiades M, Lehotay SJ, Štajnbaher D, Schenck FJ. Fast and easy multiresidue method employing acetonitrile extraction/partitioning and “dispersive solid-phase extraction” for the determination of pesticide residues in produce. J AOAC Int. 2003;86:412–31.

    CAS  Google Scholar 

  25. Lehotay SJ. Determination of pesticide residues in foods by acetonitrile extraction and partitioning with magnesium sulfate: collaborative study. J AOAC Int. 2007;90:485–520.

    CAS  Google Scholar 

  26. Herrero P, Borrull F, Pocurull E, Marcé RM. A quick, easy, cheap, effective, rugged and safe extraction method followed by liquid chromatography-(Orbitrap) high resolution mass spectrometry to determine benzotriazole, benzothiazole and benzenesulfonamidederivates in sewage sludge. J Chromatogr A. 2014;1339:34–41.

    Article  CAS  Google Scholar 

  27. Rajski T, Lozano A, Uclés A, Ferrer C, Fernández-Alba AR. Determination of pesticide residues in high oil vegetal commodities by using various multi-residue methods and clean-ups followed by liquid chromatography tandem mass spectrometry. J Chromatogr A. 2013;1304:109–20.

    Article  CAS  Google Scholar 

  28. Lozano A, Kiedrowska B, Scholten J, De Kroon M, De Kok A, Fernández-Alba AR. Miniaturisation and optimisation of the Dutch mini-Luke extraction method for implementation in the routine multi-residue analysis of pesticides in fruits and vegetables. Food Chem. 2016;192:668–81.

    Article  CAS  Google Scholar 

  29. Ghanem A, Bados P, Perreau F, Benabdallah R, Plagellat C, De Alencastro LF, et al. Multiresidue analysis of atrazine, diuron and their degradation products in sewage sludge by liquid chromatography tandem mass spectrometry. Anal Bioanal Chem. 2008;391(1):345–52.

    Article  CAS  Google Scholar 

  30. García-Valcárcel AI, Tadeo JL. A combination of ultrasonic assisted extraction with LC-MS/MS for the determination of organophosphorus pesticides in sludge. Anal Chim Acta. 2009;641(1):345–52.

    Google Scholar 

  31. Baugros J-B, Cren-Olivé C, Giroud B, Gauvrit J-Y, Lantéri P, Grenier-Loustalot M-F. Optimisation of pressurised liquid extraction by experimental design for quantification of pesticides and alkyl phenols in sludge, suspended materials and atmospheric fallout by liquid chromatography-tandem mass spectrometry. J Chromatogr A. 2009;1216(25):4941–9.

    Article  CAS  Google Scholar 

  32. SANTE/11945/2015. Guidance document on analytical quality control and method validation procedures for pesticides residues analysis in food and feed. Available from: http://ec.europa.eu/food/plant/docs/plant_pesticides_mrl_guidelines_wrkdoc_11945_en.pdf]. Accessed 14th Nov 2016

  33. García-Valcárcel AI, Tadeo JL. Determination of azoles in sewage sludge from Spanish wastewater treatment plants by liquid chromatography-tandem mass spectrometry. J Sep Sci. 2011;34(11):1228–35.

    Article  Google Scholar 

  34. Wluka A-K, Rüdel H, Pohl K, Schwarzbauer J. Analytical method development for the determination of eight biocides in various environmental compartments and application for monitoring purposes. Environ Sci Pollut Res. 2016;23(21):21894–907.

    Article  CAS  Google Scholar 

  35. Campo J, Masiá A, Blasco C, Picó Y. Occurrence and removal efficiency of pesticides in sewage treatment plants of four Mediterranean River Basins. J Hazard Mater. 2013;263:146–57.

    Article  CAS  Google Scholar 

  36. 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 

  37. European Commission. Commission Implementing Regulation (EU) no 485/2013 of 24 May 2013 amending Implementing Regulation (EU) no 540/2011, as regards the conditions of approval of the active substances clothianidin, thiamethoxam and imidacloprid, and prohibiting the use and. Off J Eur Union. 2013;139:12–26.

    Google Scholar 

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Acknowledgments

The authors wish to thank the Junta de Andalucía (Andalusian Regional Government in Spain) (RNM-1739) and the European Regional Development Fund (ERDF) for funding this investigation.

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Authors and Affiliations

  1. Plataforma Solar de Almería-CIEMAT, Carretera de Senés Km4, 04200, Tabernas, Almería, Spain

    Laura Ponce-Robles, Isabel Oller & Sixto Malato

  2. CIESOL, Joint Centre of the University of Almería-CIEMAT, Carretera de Sacramento s/n, 04120, La Cañada de San Urbano, Almería, Spain

    Laura Ponce-Robles, Gracia Rivas, Belen Esteban, Isabel Oller, Sixto Malato & Ana Agüera

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  1. Laura Ponce-Robles
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Correspondence to Ana Agüera.

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Ponce-Robles, L., Rivas, G., Esteban, B. et al. Determination of pesticides in sewage sludge from an agro-food industry using QuEChERS extraction followed by analysis with liquid chromatography-tandem mass spectrometry. Anal Bioanal Chem 409, 6181–6193 (2017). https://doi.org/10.1007/s00216-017-0558-5

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  • DOI: https://doi.org/10.1007/s00216-017-0558-5

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