The Mondego River estuary demonstrates signs of pollution, but the levels of endocrine disrupting compounds (EDCs), such as the natural (17β-estradiol and estrone) and pharmaceutical (17α-ethynylestradiol) estrogens, xenoestrogenic industrial pollutants (4-octylphenol, 4-nonylphenol, and their mono- and diethoxylates and bisphenol A), phytoestrogens (formononetin, biochanin A, daidzein, and genistein), and sitosterol were either poorly or never measured in this area. Thus, to conclude about the influx of EDCs in this estuary, water samples were taken every 2 months, during 1 year (2010) in low tide, at eight sites distributed along the estuary. Water samples (1 L) were preconcentrated in the Oasis HLB cartridges and cleaned in silica cartridges before their analysis by GC-MS. In summer, potentially hazardous amounts of estrogens (≈ 26 ng L(-1)), alkylphenols (≈ 11.5 μg L(-1)), alkylphenolethoxylates (≈ 13 μg L(-1)), and phytoestrogens (≈ 5.6 μg L(-1)) were measured. These data suggest that changes in the hydrodynamics of the estuary coupled with the increase of water temperatures interfere with the amount of EDCs in the water. Complementary physicochemical parameters also point to high levels of anthropogenic pollution in this area. Globally, the estrogenic load, expressed in ethynylestradiol equivalents, attained 71.8 ng L(-1) demonstrating that, all together, the measured EDCs pose important health risks for both biota and humans.
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.
In spite of its outstanding ecological and touristic importance the Ria Formosa Lagoon shows signs of anthropogenic pollution. Nonetheless, until the present survey no studies had ever documented the measurement of natural and pharmaceutical estrogens (17β-estradiol, estrone, and 17α-ethynylestradiol), xenoestrogenic industrial pollutants (4-octylphenol, 4-nonylphenol, and their mono and diethoxylates and bisphenol A), phytoestrogens (formononetin, biochanin A, daidzein, genistein), and sitosterol in this area. The 17 compounds measured herein are known as endocrine disrupters (EDCs) and act over the endocrine system even in few amounts (ng L ), mainly in summer, suggesting that the increase of the local number of inhabitants (tourists), the rise of the water temperature (up to 26°C), and the blooming of local flora may interfere with the water quality parameters. This makes the lagoon a potential model to study. Taking into account the data, it was concluded that there are conditions for the occurrence of endocrine disruption in aquatic animals, even in areas included in the natural park of the Formosa. Besides, both the high amounts of un-ionized ammonia (up to 0.3 mg L −1) and phosphates (up to 1.6 mg L −1 ) my pose risks for local fauna and humans.
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