Determination of pharmaceuticals, personal care products, and pesticides in surface and treated waters: method development and survey

Abstract

Water is fundamental to the existence of life since it is essential to a series of activities, such as agriculture, power generation, and public and industrial supplies. The residual water generated by these activities is released into the environment, reaches the water systems, and becomes a potential risk to nontarget organisms. This paper reports the development and validation of a quantitative method, based on solid-phase extraction and liquid chromatography tandem mass spectrometry, for the simultaneous analysis of 18 pharmaceuticals and personal care products (PPCPs) and 33 pesticides in surface and drinking waters. The accuracy of the method was determined by calculating the recoveries, which ranged from 70 to 120 % for most pesticides and PPCPs, whereas limits of quantification ranged from 0.8 to 40 ng/L. After the validation step, the method was applied to drinking and surface waters. Pesticides and PPCPs were found in concentrations lower than 135.5 ng/L. The evaluation of different water sources with regard to contamination by pesticides and PPCPs has been quite poor in southern Brazil.

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References

  1. Bach M, Letzel M, Kaul U, Forstner S, Metzner G, Klasmeier J, Reichenberger S, Frede HG (2010) Measurement and modeling of bentazone in the river Main (Germany) originating from point and non-point sources. Water Res 44(12):3725–3733

    Article  CAS  Google Scholar 

  2. Basaglia G, Pietrogrande MC (2012) Optimization of a SPME/GC/MS method for the simultaneous determination of pharmaceuticals and personal care products in waters. Chromatographia 7(8):361–370

    Article  Google Scholar 

  3. Battaglin WA, Sandstrom MW, Kuivila KM, Kolpin DW, Meyer MT (2011) Occurrence of azoxystrobin, propiconazole, and selected other fungicides in US streams, 2005–2006. Water Air Soil Pollut 218(1–4):307–322

    Article  CAS  Google Scholar 

  4. Bila DM, Dezotti M (2007) Desreguladores endócrinos no meio ambiente: efeitos e conseqüências. Quim Nova 30:651–666

    Article  CAS  Google Scholar 

  5. Bono-Blay F, Guart A, de la Fuente B, Pedemonte M, Pastor M, Borrell A, Lacorte S (2012) Survey of phthalates, alkylphenols, bisphenol A and herbicides in Spanish source waters intended for bottling. Environ Sci Pollut Res 19(8):3339–3349

    Article  CAS  Google Scholar 

  6. Buchberger WW (2007) Novel analytical procedures for screening of drug residues in water, waste water, sediment and sludge. Anal Chim Acta 593(2):129–139

    Article  CAS  Google Scholar 

  7. Cabrera LC, Caldas SS, Rodrigues S, Bianchini A, Duarte FA, Primel EG (2010) Degradation of herbicide diuron in water employing the Fe0/H2O2 system. J Braz Chem Soc 21(12):2347–2352

    Article  CAS  Google Scholar 

  8. Caldas SS, Demoliner A, Costa FP, D’Oca MGM, Primel EG (2010) Pesticide residue determination in groundwater using solid-phase extraction and high-performance liquid chromatography with diode array detector and liquid chromatography-tandem mass spectrometry. J Braz Chem Soc 21(4):642–650

    Article  CAS  Google Scholar 

  9. Caldas SS, Gonçalves FF, Primel EG, Prestes OD, Martins ML, Zanella R (2011) Modern techniques of sample preparation for pesticide residues determination in water by liquid chromatography with detection by diode array and mass spectrometry. Quim Nova 34(9):1604–1617

    Article  CAS  Google Scholar 

  10. Calza P, Medana C, Padovano E, Giancotti V, Minero C (2013) Fate of selected pharmaceuticals in river waters. Environ Sci Pollut Res. doi:10.1007/s11356-012-1097-4

  11. Capdeville MJ, Budzinski H (2011) Trace-level analysis of organic contaminants in drinking waters and groundwaters. TrAC Trends Anal Chem 30(4):586–606

    CAS  Google Scholar 

  12. Choi K, Kim Y, Park J, Park CK, Kim M, Kim HS, Kim P (2008) Seasonal variations of several pharmaceutical residues in surface water and sewage treatment plants of Han River, Korea. Sci Total Environ 405(1–3):120–128

    Article  CAS  Google Scholar 

  13. Chowdhury AZ, Jahan SA, Islam MN, Moniruzzaman M, Alam MK, Zaman MA, Karim N, Gan SH (2012) Occurrence of organophosphorus and carbamate pesticide residues in surface water samples from the Rangpur district of Bangladesh. Bull Environ Contam Toxicol 89(1):202–207

    Article  CAS  Google Scholar 

  14. Daughton CG, Ternes TA (1999) Pharmaceuticals and personal care products in the environment: agents of subtle change? Environ Health Perspect 107(Suppl 6):907

    Article  CAS  Google Scholar 

  15. Demoliner A, Caldas SS, Costa FP, Gonçalves FF, Clementin RM, Milani MR, Primel EG (2010) Development and validation of a method using spe and LC-ESI-MS-MS for the determination of multiple classes of pesticides and metabolites in water samples. J Braz Chem Soc 21(8):1424–1433

    Article  CAS  Google Scholar 

  16. Fent K, Weston AA, Caminada D (2006) Ecotoxicology of human pharmaceuticals. Aquat Toxicol 76(2):122–159

    Article  CAS  Google Scholar 

  17. Huang Q, Yu Y, Tang C, Peng X (2010) Determination of commonly used azole antifungals in various waters and sewage sludge using ultra-high performance liquid chromatography–tandem mass spectrometry. J Chromatogr A 1217(21):3481–3488

    Article  CAS  Google Scholar 

  18. IBGE (2008) Indicadores de Desenvolvimento Sustentável. Diretoria de Geociências, Coordenação de Recursos Naturais e Estudos Ambientais, Coordenação de Geogragrafia. From http://www.ibge.gov.br/home/geociencias/recursosnaturais/ids/ids2010.pdf. Accessed 15 Dec 2012

  19. IBGE (2011) Atlas de Saneamento 2011. From ftp://geoftp.ibge.gov.br/documentos/recursos_naturais/indicadores_desenvolvimento_sustentavel/2012/ids2012.pdf. Accessed 15 Oct 2012

  20. Iglesias A, Nebot C, Miranda J, Vázquez B, Cepeda A (2012) Detection and quantitative analysis of 21 veterinary drugs in river water using high-pressure liquid chromatography coupled to tandem mass spectrometry. Environ Sci Pollut Res 19(8):3235–3249

    Article  CAS  Google Scholar 

  21. Köck-Schulmeyer M, Ginebreda A, González S, Cortina JL, de Alda ML, Barceló D (2012) Analysis of the occurrence and risk assessment of polar pesticides in the Llobregat River Basin (NE Spain). Chemosphere 86(1):8–16

    Article  Google Scholar 

  22. Kroflič A, Apelblat A, Bešter-Rogač M (2012) Dissociation constants of parabens and limiting conductances of their ions in water. J Phys Chem B 116(4):1385–1392

    Article  Google Scholar 

  23. Lapworth DJ, Baran N, Stuart ME, Ward RS (2012) Emerging organic contaminants in groundwater: a review of sources, fate and occurrence. Environ Pollut 163:287–303

    Article  CAS  Google Scholar 

  24. Locatelli M, Sodré F, Jardim W (2011) Determination of antibiotics in Brazilian surface waters using liquid chromatography–electrospray tandem mass spectrometry. Arch Environ Contam Toxicol 60(3):385–393

    Article  CAS  Google Scholar 

  25. Marchesan E, Sarzi Sartori GM, de Avila LA, Machado SLO, Zanella R, Primel EG, Mussoi Macedo VR, Marchezan MG (2010) Residues of pesticides in the water of the Depression Central rivers in the State of Rio Grande do Sul, Brazil. Cienc Rural 40(5):1053–1059

    Article  Google Scholar 

  26. Munaron D, Tapie N, Budzinski H, Andral B, Gonzalez J-L (2012) Pharmaceuticals, alkylphenols and pesticides in Mediterranean coastal waters: Results from a pilot survey using passive samplers. Est Coast Shelf Sci 114:82–92. doi:10.1016/j.ecss.2011.09.009

  27. Pareja L, Colazzo M, Pérez-Parada A, Besil N, Heinzen H, Böcking B, Cesio V, Fernández-Alba AR (2012) Occurrence and distribution study of residues from pesticides applied under controlled conditions in the field during rice processing. J Agric Food Chem 60(18):4440–4448

    Article  CAS  Google Scholar 

  28. Pedrouzo M, Borrull F, Marcé RM, Pocurull E (2009) Ultra-high-performance liquid chromatography–tandem mass spectrometry for determining the presence of eleven personal care products in surface and wastewaters. J Chromatogr A 1216(42):6994–7000

    Article  CAS  Google Scholar 

  29. Pinhancos R, Maass S, Ramanathan DM (2011) High-resolution mass spectrometry method for the detection, characterization and quantitation of pharmaceuticals in water. J Mass Spectrom 46(11):1175–1181

    Article  CAS  Google Scholar 

  30. Primel EG, Caldas SS, Escarrone ALV (2012) Multi-residue analytical methods for the determination of pesticides and PPCPs in water by LC-MS/MS: a review. Cent Eur J Chem 10(3):876–899

    Article  Google Scholar 

  31. Richardson SD (2009) Water analysis: emerging contaminants and current issues. Anal Chem 81(12):4645–4677

    Article  CAS  Google Scholar 

  32. Sodré F, Locatelli M, Jardim W (2010) Occurrence of emerging contaminants in Brazilian drinking waters: a sewage-to-tap issue. Water Air Soil Pollut 206(1):57–67

    Article  Google Scholar 

  33. Struger J, Grabuski J, Cagampan S, Rondeau M, Sverko E, Marvin C (2011) Occurrence and distribution of sulfonylurea and related herbicides in central Canadian surface waters 2006–2008. Bull Environ Contam Toxicol 87(4):420–425

    Article  CAS  Google Scholar 

  34. Wick A, Fink G, Ternes TA (2010) Comparison of electrospray ionization and atmospheric pressure chemical ionization for multi-residue analysis of biocides, UV-filters and benzothiazoles in aqueous matrices and activated sludge by liquid chromatography–tandem mass spectrometry. J Chromatogr A 1217(14):2088–2103

    Article  CAS  Google Scholar 

  35. Xu Y, Luo F, Pal A, Gin KYH, Reinhard M (2011) Occurrence of emerging organic contaminants in a tropical urban catchment in Singapore. Chemosphere 83(7):963–969

    Article  CAS  Google Scholar 

  36. Zarn JA, Brüschweiler BJ, Schlatter JR (2003) Azole Fungicides Affect Mammalian Steroidogenesis by Inhibiting Sterol 14α-Demethylase and aromatase Environ Health Perspect. 111(3):255–261

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Acknowledgments

The authors acknowledge the financial support and fellowships granted by the Brazilian agencies CAPES, FINEP, CORSAN, and FURG. Part of this study was supported by a grant from the Brazilian Agency FAPERGS/CNPq (process number 010/0022-0), CNPq/CAPES (process number 552318/2011-6), CNPq (process number 477083/2011-00), FAPERGS (process number 11/0816-3), and FAPERGS/PROCOREDES (process number 0905342). E.G. Primel got a productivity research fellowship from the Brazilian Agency CNPq (DT 311605/2009-5).

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Correspondence to Ednei Gilberto Primel.

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Responsible editor: Hongwen Sun

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Caldas, S.S., Bolzan, C.M., Guilherme, J.R. et al. Determination of pharmaceuticals, personal care products, and pesticides in surface and treated waters: method development and survey. Environ Sci Pollut Res 20, 5855–5863 (2013). https://doi.org/10.1007/s11356-013-1650-9

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Keywords

  • Pesticides
  • PPCPs
  • LC-MS/MS
  • Environmental waters