Spatial distribution and quantification of endocrine-disrupting chemicals in Sado River estuary, Portugal
The important Portuguese Sado River estuary has never been investigated for the presence of potentially endocrine-disrupting chemicals (EDCs), such as natural estrogens (estradiol, estrone), pharmaceutical estrogens (17α-ethynylestradiol), phytoestrogens (daidzein, genistein and biochanin A), or industrial chemicals (4-octylphenol, 4-nonylphenol, and bisphenol A). Thus, the main objective of this study was to evaluate their presence at 13 sampling points distributed between both the industrial and the natural reserve areas of the estuary, zones 1 and 2, respectively. For that, water samples collected in summer and winter were processed by solid phase extraction and analyzed by high-performance liquid chromatography with photodiode array detection and gas chromatography–mass spectroscopy. Results showed that estrone, ethynylestradiol, all the aforementioned phytoestrogens as well as bisphenol A and 4-octylphenol were found in zone 1. In zone 2, neither estrogens nor 4-OP were found. However, in the same zone, daidzein (500 ng/L) and genistein (320 ng/L) attained their highest levels in summer, whereas biochanin A peaked in winter (170 ng/L). Furthermore, bisphenol A was also found in some areas of zone 2, but showed similar concentrations in both surveys (about 220 ng/L). This study demonstrated that the Sado River estuary had low EDCs levels, suggesting that the Sado’s high hydrodynamic activity may be involved in the dilution of local pollution. It was suggested that at the current levels of concentrations, all assayed EDCs are unlikely to individually cause endocrine disruption in local animals. However, under a continuous exposure scenario, an additive and/or synergistic action of the estrogenic chemicals load can not be excluded, and so, continuous monitoring is advisable.
KeywordsBiochanin-A Bisphenol-A Daidzein Endocrine-disrupting chemicals (EDCs) Genistein Phytoestrogens Sado River estuary
- Almeida, C., Serôdio, P., Florêncio, M. H., & Nogueira, J. M. F. (2007). New strategies to screen for endocrine-disrupting chemicals in the Portuguese marine environment utilizing large volume injection-capillary gas chromatography-mass spectrometry combined with retention time locking libraries (LVI-GC-MS-RTL). Analytical and Bioanalytical Chemistry, 387, 2569–2583. doi:10.1007/s00216-006-1101-2.CrossRefGoogle Scholar
- Ballesteros, O., Zafra, A., Navalon, A., & Vilchez, J. L. (2006). Sensitive gas chromatographic-mass spectrometric method for the determination of phthalate esters, alkylphenols, bisphenol A and their chlorinated derivatives in wastewater samples. Journal of Chromatography. A, 1121, 154–162. doi:10.1016/j.chroma.2006.04.014.CrossRefGoogle Scholar
- Catarino, J., Peneda, M. C., & Santana, F. (1987). Estudo do impacto da indústria no estuário do Rio Sado. Estimativas da poluição afluente. Instituto Nacional de Engenharia e Tecnologia Industrial, Lisbon, Portugal: DEII, INETI.Google Scholar
- Ferreira, J. G., Nobre, A. M., Sirnas, T. C., Silva, M. C., Newton, A., Bricker, S. B., et al. (2006). A methodology for defining homogeneous water bodies in estuaries—application to the transitional systems of the EU Water Framework Directive. Estuarine, Coastal and Shelf Science, 66, 468–482. doi:10.1016/j.ecss.2005.09.016.CrossRefGoogle Scholar
- Ferreira, J. G., Simas, T., Schifferegger, K., & Lencart-Silva, J. (2002). Identification of sensitive areas and vulnerable zones in four Portuguese Estuaries. INAG–Instituto da Água, IMAR–Institute of Marine Research.Google Scholar
- Ferreira, A. M., & Vale, C. (2001). Seasonal and inter-annual variations of PCB and DDT contents in the oyster Crassostrea angulata from the Sado Estuary (Portugal). Ciencias Marinas, 27, 255–268.Google Scholar
- International Conference on Harmonisation ICH (1996). Validation of analytical procedures: Methodology, Q. 2B (CPMP/ICH/281/96). London: The European Agency for the Evaluation of Medicinal Products.Google Scholar
- Jobling, S., Beresford, N., Nolan, M., Rodgers-Gray, T., Brighty, G. C., Sumpter, J. P., et al. (2002). Altered sexual maturation and gamete production in wild roach (Rutilus rutilus) living in rivers that receive treated sewage effluents. Biology of Reproduction, 66, 272–281. doi:10.1095/biolreprod66.2.272.CrossRefGoogle Scholar
- Kiparissis, Y., Balch, G. C., Metcalfe, T. L., & Metcalfe, C. D. (2003). Effects of the isoflavones genistein and equol on the gonadal development of Japanese medaka (Oryzias latipes). Environmental Health Perspectives, 111, 1158–1163.Google Scholar
- Lagana, A., Bacaloni, A., De Leva, I., Faberi, A., Fago, G., & Marino, A. (2004). Analytical methodologies for determining the occurrence of endocrine disrupting chemicals in sewage treatment plants and natural waters. Analytica Chimica Acta, 501, 79–88. doi:10.1016/j.aca.2003.09.020.CrossRefGoogle Scholar
- Moreira, S. M., Lima, I., Ribeiro, R., & Guilhermino, L. (2006). Effects of estuarine sediment contamination on feeding and on key physiological functions of the polychaete Hediste diversicolor: Laboratory and in situ assays. Aquatic Toxicology (Amsterdam, Netherlands), 78, 186–201. doi:10.1016/j.aquatox.2006.03.001.Google Scholar
- Ribeiro, C., Tiritan, M. E., Rocha, E., & Rocha, M. J. (2007). Development and validation of a HPLC-DAD method for determination of several endocrine disrupting compounds in estuarine water. Journal of Liquid Chromatography & Related Technologies, 30, 2729–2746. doi:10.1080/10826070701560652.CrossRefGoogle Scholar
- Ribeiro, C., Pardal, M. A., Martinho, F., Margalho, R., Tiritan, M. E., Rocha, E., et al. (2008a). Distribution of endocrine disruptors in the Mondego River estuary, Portugal. Environmental Monitoring and Assessment, (in press). doi:10.1007/s10661-10008-10192-y.
- Ribeiro, C., Tiritan, M. E., Rocha, E., & Rocha, M. J. (2008b). Seasonal and spatial distribution of several endocrine disrupting compounds in the Douro River estuary, Portugal. Archives of Environmental Contamination and Toxicology, (in press). doi:10.1007/s00244-008-9158-x.
- Shareef, A., Angove, M. J., & Wells, J. D. (2006). Optimization of silylation using N-methyl-N-(trimethylsilyl)-trifluoroacetamide, N,O-bis-(trimethylsilyl)-trifluoroacetamide and 4N4-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide for the determination of the estrogens estrone and 17[alpha]-ethinylestradiol by gas chromatography–mass spectrometry. Journal of Chromatography. A, 1108, 121–128. doi:10.1016/j.chroma.2005.12.098.CrossRefGoogle Scholar
- Silva, E., Batista, S., Viana, P., Antunes, P., Serôdio, L., Cardoso, A. T., et al. (2006). Pesticides and nitrates in groundwater from oriziculture areas of the ‘Baixo Sado’ region (Portugal). International Journal of Environmental Analytical Chemistry, 86, 955–972. doi:10.1080/03067310600833336.CrossRefGoogle Scholar
- Silveira, M. (2007). Identification of endocrine disrupters in superficial waters of Douro River estuary. Dissertation, University of Porto, Portugal.Google Scholar
- Vasconcelos, R. P., Reis-Santos, P., Fonseca, V., Maia, A., Ruano, M., Franca, S., et al. (2007). Assessing anthropogenic pressures on estuarine fish nurseries along the Portuguese coast: A multi-metric index and conceptual approach. The Science of the Total Environment, 374, 199–215. doi:10.1016/j.scitotenv.2006.12.048.CrossRefGoogle Scholar
- Vethaak, A. D., Lahr, J., Schrap, S. M., Belfroid, A. C., Rijs, G. B. J., Gerritsen, A., et al. (2005). An integrated assessment of estrogenic contamination and biological effects in the aquatic environment of The Netherlands. Chemosphere, 59, 511–524. doi:10.1016/j.chemosphere.2004.12.053.CrossRefGoogle Scholar