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Pollution by oestrogenic endocrine disruptors and β-sitosterol in a south-western European river (Mira, Portugal)

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Abstract

The Mira River is a Portuguese water body widely known for its wilderness and is advertised as one of the less polluted European rivers. On this presumption, the levels of endocrine-disrupting compounds (EDCs) in Mira waters were never measured. However, because environmentalists have claimed that the Mira could be moderately polluted, a range of 17 EDCs were measured not only at the estuary but also along the river. The targeted EDCs included natural and pharmaceutical oestrogens (17β-oestradiol, oestrone and 17α-ethynylestradiol), industrial/household pollutants (octylphenols, nonylphenols and their monoethoxylates and diethoxylates and bisphenol A), phytoestrogens (formononetin, biochanin A, daidzein, genistein) and the phytosterol sitosterol (SITO). For this propose, waters from six sampling sites were taken every 2 months, over a 1-year period (2011), and analysed by gas chromatography–mass spectrometry. Unexpectedly high levels of oestrogens and of industrial/household pollutants were measured at all sampling sites, including those located inside natural protected areas. Indeed, the annual average sum of EDCs was ≈57 ng/L for oestrogens and ≈1.3 μg/L for industrial/household chemicals. In contrast, the global average levels of phytoestrogens (≈140 ng/L) and of SITO (≈295 ng/L) were lower than those reported worldwide. The EDC concentrations were normalised for ethynylestradiol equivalents (EE2eq). In view of these, the oestrogenic load of the Mira River attained ≈47 ng/L EE2eq. In addition, phosphates were above legal limits at both spring and summer (>1 mg/L). Overall, data show EDCs at toxicant relevant levels in the Mira and stress the need to monitor rivers that are allegedly less polluted.

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Acknowledgments

This study was partially supported by the European Regional Development Fund (ERDF), through the Operational Competitiveness Program (COMPETE), and by Portuguese funds, through the Foundation for Science and Technology (FCT), via projects PTDC/MAR/70436/2006 and PEst-C/MAR/LA0015/2013.

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Correspondence to Maria João Rocha.

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Table A

Figures referring to intra and inter-day precision, accuracy and recovery data for all EDCs spiked at three different levels of concentration (low, medium and high) in artificial coastal water (Rocha et al. 2013c). (DOCX 23 kb)

Table B

Analytical characteristics of the optimized GC-MS method (Rocha et al. 2013c): calibration equations, coefficients of determination (r2), method detection limit (MDL), time of retention (tR), and quantification / diagnostic ions used in GC-MS analysis. Inside brackets is referred to the relative abundance of ions (m/z) for each target EDC. (DOCX 17 kb)

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Rocha, M.J., Cruzeiro, C., Reis, M. et al. Pollution by oestrogenic endocrine disruptors and β-sitosterol in a south-western European river (Mira, Portugal). Environ Monit Assess 188, 240 (2016). https://doi.org/10.1007/s10661-016-5236-0

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