Environmental Science and Pollution Research

, Volume 20, Issue 8, pp 5855–5863 | Cite as

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

  • Sergiane Souza Caldas
  • Cátia Marian Bolzan
  • Juliana Rocha Guilherme
  • Maria Angelis Kisner Silveira
  • Ana Laura Venquiaruti Escarrone
  • Ednei Gilberto PrimelEmail author
Research Article


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.


Pesticides PPCPs LC-MS/MS Environmental waters 



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).


  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):3725–3733CrossRefGoogle 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):361–370CrossRefGoogle 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):307–322CrossRefGoogle Scholar
  4. Bila DM, Dezotti M (2007) Desreguladores endócrinos no meio ambiente: efeitos e conseqüências. Quim Nova 30:651–666CrossRefGoogle 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):3339–3349CrossRefGoogle 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):129–139CrossRefGoogle 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):2347–2352CrossRefGoogle 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):642–650CrossRefGoogle 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):1604–1617CrossRefGoogle 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):586–606Google 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):120–128CrossRefGoogle 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):202–207CrossRefGoogle 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):907CrossRefGoogle 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):1424–1433CrossRefGoogle Scholar
  16. Fent K, Weston AA, Caminada D (2006) Ecotoxicology of human pharmaceuticals. Aquat Toxicol 76(2):122–159CrossRefGoogle 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):3481–3488CrossRefGoogle Scholar
  18. IBGE (2008) Indicadores de Desenvolvimento Sustentável. Diretoria de Geociências, Coordenação de Recursos Naturais e Estudos Ambientais, Coordenação de Geogragrafia. From Accessed 15 Dec 2012
  19. 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):3235–3249CrossRefGoogle Scholar
  20. 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):8–16CrossRefGoogle Scholar
  21. 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):1385–1392CrossRefGoogle Scholar
  22. Lapworth DJ, Baran N, Stuart ME, Ward RS (2012) Emerging organic contaminants in groundwater: a review of sources, fate and occurrence. Environ Pollut 163:287–303CrossRefGoogle Scholar
  23. 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):385–393CrossRefGoogle Scholar
  24. 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):1053–1059CrossRefGoogle Scholar
  25. 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
  26. 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):4440–4448CrossRefGoogle Scholar
  27. 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):6994–7000CrossRefGoogle Scholar
  28. 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):1175–1181CrossRefGoogle Scholar
  29. 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):876–899CrossRefGoogle Scholar
  30. Richardson SD (2009) Water analysis: emerging contaminants and current issues. Anal Chem 81(12):4645–4677CrossRefGoogle Scholar
  31. 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):57–67CrossRefGoogle Scholar
  32. 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):420–425CrossRefGoogle Scholar
  33. 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):2088–2103CrossRefGoogle Scholar
  34. 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):963–969CrossRefGoogle Scholar
  35. Zarn JA, Brüschweiler BJ, Schlatter JR (2003) Azole Fungicides Affect Mammalian Steroidogenesis by Inhibiting Sterol 14α-Demethylase and aromatase Environ Health Perspect. 111(3):255–261Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  • Sergiane Souza Caldas
    • 1
  • Cátia Marian Bolzan
    • 1
  • Juliana Rocha Guilherme
    • 1
  • Maria Angelis Kisner Silveira
    • 1
  • Ana Laura Venquiaruti Escarrone
    • 1
  • Ednei Gilberto Primel
    • 1
    Email author
  1. 1.Laboratório de Análises de Compostos Orgânicos e Metais, Escola de Química e AlimentosUniversidade Federal do Rio GrandeRio GrandeBrazil

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