Abstract
As a part of a project aiming to assess the potential toxicological effects of contaminants in aquatic ecosystems, the objective of this work was to determine the occurrence of several selected endocrine-disrupting compounds in water and sediment and to estimate the estrogenicity of the water. The study consisted of four sampling campaigns at seven sampling points in the lower Llobregat catchment area (NE Spain). Water and sediment samples underwent chemical target analysis for 19 steroid estrogens and alkylphenols, which are known to be endocrine-disrupting compounds. In this study, the only estrogens detected in the water samples were estrone and estrone-sulfate, which were found at low levels (2–5 ng l−1). The alkylphenolic compound showing the highest concentrations was nonylphenol di-ether carboxylate (NP2EC), which was found at levels up to 30.62 µg l−1 in water samples and 535 ng g−1 in sediment samples. K d was determined for several alkylphenolic compounds and showed the expected trend of decreasing K d with increasing polarity. The concentrations of nonylphenol and octylphenol only exceeded the annual average of the European Union’s environmental quality standards (EQS) in one sampling point. However, the calculated estrogenic potential surpassed the expected effect concentration in several sampling points, indicating a potential risk. Therefore, we recommend that future EQS include short-chain alkylphenol ethoxylates and carboxylates.
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Schomberg DW, Couse JF, Mukherjee A, Lubahn DB, Sar M, Mayo KE, Korach KS (1999) Targeted disruption of the estrogen receptor-α gene in female mice: characterization of ovarian responses and phenotype in the adult. Endocrinology 140:2733–2744
Soto AM, Maffini MV, Schaeberle CM, Sonnenschein C (2006) Strengths and weaknesses of in vitro assays for estrogenic and androgenic activity. Best Pract Res Clin Endocrinol Metab 20:15–33
Wang L, Andersson S, Warner M, Gustafsson JA (2003) Estrogen receptor (ER)β knockout mice reveal a role for ERβ in migration of cortical neurons in the developing brain. Proc Natl Acad Sci U S A 100:703–708
Petrovic M, Diaz A, Ventura F, Barcelo D (2003) Occurrence and removal of estrogenic short-chain ethoxy nonylphenolic compounds and their halogenated derivatives during drinking water production. Environ Sci Technol 37:4442–4448
Rodriguez-Mozaz S, López De Alda MJ, Barceló D (2004) Monitoring of estrogens, pesticides and bisphenol A in natural waters and drinking water treatment plants by solid-phase extraction–liquid chromatography–mass spectrometry. J Chrom A 1045:85–92
Rivera J, Caixach J, Ventura F, Espadaler I (1985) Herbicide and surfactant spill analysis of an industrial waste dumping at Llobregat river (Spain). Chemosphere 14:395–402
Quintana J, Martí I, Ventura F (2001) Monitoring of pesticides in drinking and related waters in NE Spain with a multiresidue SPE-GC-MS method including an estimation of the uncertainty of the analytical results. J Chrom A 938:3–13
Eichhorn P, Knepper TP, Ventura F, Diaz A (2002) The behavior of polar aromatic sulfonates during drinking water production: a case study on sulfophenyl carboxylates in two European waterworks. Water Res 36:2179–2186
Céspedes R, Lacorte S, Raldúa D, Ginebreda A, Barceló D, Piña B (2005) Distribution of endocrine disruptors in the Llobregat River basin (Catalonia, NE Spain). Chemosphere 61:1710–1719
López de Alda MJ, Gil A, Paz E, Barcelo D (2002) Occurrence and analysis of estrogens and progestogens in river sediments by liquid chromatography–electrospray–mass spectrometry. Analyst 127:1299–1304
Garcia-Reyero N, Grau E, Castillo M, De Alda MJL, Barcelo D, Pina B (2001) Monitoring of endocrine disruptors in surface waters by the yeast recombinant assay. Environ Toxicol Chem 20:1152–1158
Petrovic M, Sole M, Lopez de Alda MJ, Barcelo D (2002) Endocrine disruptors in sewage treatment plants, receiving river waters, and sediments: Integration of chemical analysis and biological effects on feral carp. Environ Toxicol Chem 21:2146–2156
Sole M, de Alda MJL, Castillo M, Porte C, Ladegaard-Pedersen K, Barcelo D (2000) Estrogenicity determination in sewage treatment plants and surface waters from the Catalonian area (NE Spain). Environ Sci Technol 34:5076–5083
Petrovic M, Diaz A, Ventura F, Barcelo D (2001) Simultaneous determination of halogenated derivatives of alkylphenol ethoxylates and their metabolites in sludges, river sediments, and surface, drinking, and wastewaters by liquid chromatography–mass spectrometry. Anal Chem 73:5886–5895
Petrovic M, Eljarrat E, Lopez De Alda MJ, Barcelo D (2002) Recent advances in the mass spectrometric analysis related to endocrine disrupting compounds in aquatic environmental samples. J Chrom A 974:23–51
Petrovic M, Lacorte S, Viana P, Barceló D (2002) Pressurized liquid extraction followed by liquid chromatography–mass spectrometry for the determination of alkylphenolic compounds in river sediment. J Chromatogr A 959:15–23
Kuster M, Azevedo DA, López MJ, de Alda FR, Neto A, Barceló D (2009) Analysis of phytoestrogens, progestogens and estrogens in environmental waters from Rio de Janeiro (Brazil). Environ Int 35:997–1003
Gonzalez S, Petrovic M, Barcelo D (2004) Simultaneous extraction and fate of linear alkylbenzene sulfonates, coconut diethanol amides, nonylphenol ethoxylates and their degradation products in wastewater treatment plants, receiving coastal waters and sediments in the Catalonian area (NE Spain). J Chrom A 1052:111–120
Kuster M, López de Alda MJ, Hernando MD, Petrovic M, Martín-Alonso J, Barceló D (2008) Analysis and occurrence of pharmaceuticals, estrogens, progestogens and polar pesticides in sewage treatment plant effluents, river water and drinking water in the Llobregat river basin (Barcelona, Spain). J Hydrol 358:112–123
Petrovic M, Fernandez-Alba AR, Borrull F, Marce RM, Mazo EG, Barcelo D (2002) Occurrence and distribution of nonionic surfactants, their degradation products, and linear alkylbenzene sulfonates in coastal waters and sediments in Spain. Environ Toxicol Chem 21:37–46
Rodriguez-Mozaz S, de Alda MJL, Barcelo D (2004) Picogram per liter level determination of estrogens in natural waters and waterworks by a fully automated on-line solid-phase extraction–liquid chromatography–electrospray tandem mass spectrometry method. Anal Chem 76:6998–7006
Rodriguez-Mozaz S, Lopez de Alda MJ, Barcelo D (2006) Fast and simultaneous monitoring of organic pollutants in a drinking water treatment plant by a multi-analyte biosensor followed by LC-MS validation. Talanta 69:377–384
Petrovic M, Barceló D (2004) Fate and removal of surfactants and related compounds in wastewaters and sludges. In: Barceló D (ed) The handbook of environmental chemistry, vol 5, part 1. Springer, Berlin
European Commission (2008) Directive 2008/105/EC of the European Parliament and of the Council 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
European Commission (2000) Directive 2000/60/EC of the European Parliament and of the Council establishing a framework for the Community action in the field of water policy
Weiner E (2000) Applications of environmental chemistry: a practical guide for environmental professionals. CRC, Florida
Meylan WM, Howard PH (1995) Atom/fragment contribution method for estimating octanol–water partition coefficients. J Pharm Sci 84:83–92
Rutishauser BV, Pesonen M, Escher BI, Ackermann GE, Aerni HR, Suter MJF, Eggen RIL (2004) Comparative analysis of estrogenic activity in sewage treatment plant effluents involving three in vitro assays and chemical analysis of steroids. Environ Toxicol Chem 23:857–864
Hansen PD, Dizer H, Hock B, Marx A, Sherry J, McMaster M, Blaise C (1998) Vitellogenin—a biomarker for endocrine disruptors. TrAC 17:448–451
Purdom CE, Hardiman PA, Bye VVJ, Eno NC, Tyler CR, Sumpter JP (1994) Estrogenic effects of effluents from sewage treatment works. Chem Ecol 8:275–285
Legler J, Dennekamp M, Vethaak AD, Brouwer A, Koeman JH, van der Burg B, Murk AJ (2002) Detection of estrogenic activity in sediment-associated compounds using in vitro reporter gene assays. Sci Total Environ 293:69–83
Song M, Xu Y, Jiang Q, Lam PKS, O’Toole DK, Giesy JP, Jiang G (2006) Measurement of estrogenic activity in sediments from Haihe and Dagu River, China. Environ Int 32:676–681
Viganò L, Benfenati E, Cauwenberge AV, Eidem JK, Erratico C, Goksoyr A, Kloas W, Maggioni S, Mandich A, Urbatzka R (2008) Estrogenicity profile and estrogenic compounds determined in river sediments by chemical analysis, ELISA and yeast assays. Chemosphere 73:1078–1089
Duft M, Schulte-Oehlmann U, Weltje L, Tillmann M, Oehlmann J (2003) Stimulated embryo production as a parameter of estrogenic exposure via sediments in the freshwater mudsnail Potamopyrgus antipodarum. Aquat Toxicol 64:437–449
Acknowledgments
This work has been supported by the EU Project: MODELKEY [GOCE 511237] and by the Spanish Ministry of Science and Innovation (CTM2005-24255-E, BIO2005-00840, CTM2006-26227-E/TECNO, and CGL2007-64551/HID). Cristina Postigo acknowledges the European Social Fund and AGAUR (Generalitat de Catalunya, Spain) for their economical support through the FI pre-doctoral grant. The paper reflects the authors’ views only. The EU is not liable for any use that may be made of the information contained in it.
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Brix, R., Postigo, C., González, S. et al. Analysis and occurrence of alkylphenolic compounds and estrogens in a European river basin and an evaluation of their importance as priority pollutants. Anal Bioanal Chem 396, 1301–1309 (2010). https://doi.org/10.1007/s00216-009-3358-8
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DOI: https://doi.org/10.1007/s00216-009-3358-8