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The concentrations of seventeen endocrine disruptor compounds (EDCs) that included oestrogens, phytoestrogens, sitosterol, and banned industrial pollutants were investigated at ten sites of the Douro River estuary. Surface waters were collected during 2019. After evaluating the physicochemical data (ammonia, nitrates, nitrites and phosphates), the waters were filtrated and submitted to solid-phase extraction (SPE) to extract and pre-concentrate (4000-fold) the EDCs. The extracts were derivatized with BSTFA + 1% TMS and analysed by gas chromatography-mass spectrometry (GC-MS). All EDCs showed a high detection rate (97%, on average), exhibiting ubiquity in this estuary. The finding of biologically relevant amounts of oestrogens (up to 8.5 ng/L for oestradiol, E2), phytoestrogens (up to 827 ng/L for biochanin A, BIO-A) and industrial pollutants (up to 2.7 µg/L for nonylphenol di-ethoxylated, NP2EO) strongly support ongoing risks of endocrine disruption for the local aquatic wildlife. Globally, there was an E2-equivalents (E2-EQs) concentration of 25 ng/L and a hazard index (HI) of 26, which further indicates considerable potential for adverse effects on local biota. Moreover, the physicochemical data suggest direct sewage discharges. Beyond possible toxicological effects on fauna, the detected contaminants may pose risks to humans via direct contact (bathing at local fluvial beaches) or by ingestion (local fish). [ABSTRACT FROM AUTHOR]

Estrone, 17β-estradiol, 17α-ethynylestradiol, alkylphenols and alkylphenol ethoxylates, are endocrine disruptor compounds. In Portugal, the report of male fish feminization in Minho, Ave and Mondego River estuaries made pertinent their evaluation in surface water samples. Data, got by specific enzyme-linked immunosorbent assays, showed that estrogens concentrations were lower in Minho than in Ave or Mondego estuaries: [Estrone] > [17β-estradiol] > [17α-ethynylestradiol] (p < 0.05). Converting estrogen concentrations in 17α-ethynylestradiol equivalents, the contribution of estrogens was 1.3 ng/L, 3.5 ng/L, and 2.4 ng/L, respectively, for Minho, Ave, and Mondego estuaries stressing out a high risk for local aquatic species. The concentrations of alkylphenols and alkylphenol ethoxylates were lower at both Minho and Mondego estuaries ≈600 ng/L and 2700 ng/L, respectively than at the Ave, ≈1070 ng/L and 4855 ng/L (p < 0.05). In conclusion, this study reports the first systematic data about the presence of the targeted endocrine disruptor compounds in the Minho River estuary and, in parallel, provides new information about their concentrations in two other habitats previously monitored. This study also shows that in Ave and Mondego estuaries the concentrations of industrial estrogens were still excessive, whereas the load of the pure estrogens has decreased significantly facing previous surveys. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

A gas chromatography with mass spectrometric detection (GC-MS) method was developed and optimized for the determination of 17 endocrine disrupting compounds (EDCs) in coastal water samples. The evaluated EDCs were from different origins and included estrogens, bisphenol A, alkylphenolethoxylates, alkylphenols, phytoestrogens and sitosterol (SITO). The EDCs were extracted from samples using Oasis HLB (Hydrophilic--Lipophilic Balance) cartridges and derivatized with N,Obis( trimethylsilyl)trifluoroacetamide (BSTFA) added with 1% trimethylchlorosilane (TMCS). The validation parameters revealed that this method was highly specific for all assayed compounds (>99%) and the linearity of the calibration curves showed a correlation higher than 0.99. The detection limits were at low ng/L level and the recovery rates were higher than 70%. The performance of the method was checked using coastal water samples taken every 2 months during 2009-2010 from the Douro River estuary and the Porto coastline (Portugal). These data revealed that approximately 98.0% of the analyzed compounds showed levels above their limits of detection (LODs). The measured estrogens (2-20 ng/L) and industrial pollutants (up to 1.1 μg/L) were in biologic hazardous concentrations. Besides, a clear seasonal pattern of fluctuation was established for phytoestrogens and SITO. The physicochemical data, namely the amounts of nitrates, nitrites and phosphorous, confirmed the low water quality of this area. [ABSTRACT FROM AUTHOR]

The Ave River flows through the most urbanized and industrialized Porto district areas. Despite ovotestis was recently reported in male fish from the estuary, no data exist on the water levels 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, and genistein), and sitosterol. Absence of analyses applies to the river, estuary, and nearby coastline. Those compounds mimic the action of endogenous estradiol, being well-recognized endocrine disrupters (EDCs). To conclude about suspected influxes of estrogenic EDCs into the river and coastline, water samples were taken at eight sites every two months, during one year (2010), at low tide. Data showed ubiquitous presence of potentially hazardous amounts of estrogens (particularly ethynylestradiol, up to 10 ng L−1), nonylphenol (up to 250 ng L−1), and sitosterol (up to 6 μg L−1), which helps explaining the ovotestis emergence in local fish. Also, because physicochemical parameters used in water quality evaluation, such as pH, dissolved oxygen, nitrates, and nitrites levels, were within legal limits – suggesting good quality – our study supports that assessment of human and environmental risks by targeting surface waters requires integrating EDCs monitoring in routine analyses. [ABSTRACT FROM AUTHOR]

The Sado waters show signs of anthropogenic pollution. However, hardly any information exists on the levels of endocrine disrupters (EDCs) such as estrogens (17β-estradiol, estrone and 17α-ethynylestradiol) and there is no information at all on xenoestrogenic industrial pollutants (4-octylphenol, 4-nonylphenol and their mono and diethoxylates and bisphenol A). Moreover, data on plant derived phytoestrogens (formononetin, biochanin A, daidzein, genistein) and sitosterol are scarce or inexistent. To assess on the suspected influx of EDCs in this aquatic system, water samples were taken every two months, during 2010, at nine sites distributed along the Sado Estuary and River (Alcácer do Sal) being afterward analyzed by GC-MS. Data showed the ubiquitous presence of potentially hazardous amounts of estrogens (mainly of estrone and estradiol, reaching over 10 ng L−1), nonylphenol diethoxylate (up to 900 ng L−1) and nonylphenol (up to 230 ng L−1). It was concluded that there are conditions for the occurrence of endocrine disruption in local aquatic animals, even in areas included inside the Natural Reserve. Moreover, a clear seasonal pattern of fluctuation was found for phytoestrogens and sitosterol. Besides, there were high amounts of unionized ammonia (up to 0.6 mg L−1) and phosphates (up to 3.2 mg L−1) suggesting that the current status poses risks for local fauna and humans. [ABSTRACT FROM PUBLISHER]

The Leça River and two beaches close to the north and south margins of the estuary, nowadays an important seaport harbor, show signs of contamination. However, the chemical nature of that contamination is uncertain. Therefore, this study checked for the presence of 11 endocrine disrupting compounds (EDCs) of animal (17β-estradiol and estrone), pharmaceutical (17α-ethynylestradiol), and industrial (alkylphenols, alkylphenol ethoxylates, and bisphenol A) origins in water samples collected from six points at the river gradient and at two sites in the coastline (Atlantic Ocean). Along with the EDCs, evaluated by gas chromatography – mass spectroscopy (GC-MS) during spring, summer, and autumn, physico-chemical parameters were also assessed and particular attention was given to dissolved oxygen (DO) levels. Data showed the presence of high amounts of estrogens (up to 10 ng L−1 for estrone) and industrial compounds (up to 2 µg L−1 for the nonylphenol ethoxylates) at both river and seacoast. Along with this, clear signs of hypoxia were found in the river (DO < 3 mg L−1 at several sampling sites). Taking into account these issues, it was concluded that there are local conditions for the occurrence of endocrine disruption in aquatic animals. [ABSTRACT FROM PUBLISHER]

Previous studies in the Douro River estuary, based on occasional sampling, showed the presence of several estrogenic disrupting chemicals (EDCs). In sequence, we hypothesized that such type of pollution was more likely an enduring issue than an occasional phenomenon, and that it may even affect recreational beaches in each side of the estuarine mouth. Thus to conclude about the continuous influx of EDCs, water samples were taken twice a day, once per a week, from March to May of 2009, at four sites within the estuary and at two sites in the coastline. After solid-phase extraction, the extracts were prepared for GC-MS analysis of 11 reference EDCs. These embraced natural and pharmaceutical estrogens (17β-estradiol, estrone and 17α-ethynylestradiol) and xenoestrogenic industrial pollutants (4-octylphenol, 4-nonylphenol, and their mono and diethoxylates and bisphenol A). Data showed the ubiquitous presence of potentially hazardous amounts of natural estrogens (particularly of estradiol, ca 5.5 ng L−1) and persistent organic pollutants such as nonylphenol mono (up to 550 ng L−1) and diethoxylate (up to 2000 ng L−1). It was concluded that the targeted area is continuously polluted by the assayed EDCs, and as a consequence, conditions exist for endocrine disturbance in the biota by chronic exposure to EDCs. [ABSTRACT FROM PUBLISHER]

This paper describes the development and validation of a GC-MS method which allows the simultaneous quantification of 11 endocrine disrupting compounds (EDCs) in surface water samples from both estuary and sea. The analysed EDCs are oestrone (E1), 17β-estradiol (E2), 17α-ethynylestradiol (EE2), 4-tert-octylphenol, 4-n-octylphenol, 4-nonylphenol, bisphenol A and finally, mono and diethoxylates of 4-nonylphenol and 4-octylphenol. The method includes the pre-concentration of water samples, 1000-fold factor, in OASIS HLB cartridges by solid phase extraction, the derivatisation of all EDCs by N,O-bis(trimethylsilyl)trifluoroacetamide added with 1% trimethylchlorosilane and pyridine (at 65°C for 30 min) and, finally the stabilisation of the EDCs-silylated derivatives, in hexane, for 72 h. The validation parameters revealed that this method was highly specific for all target compounds using real samples. The linearity of the calibration curves (r 2) showed correlation factors higher than 0.990. The detection limits ranged from 0.10 to 1.45 ng L−1, depending on each analysed compound, and recoveries were satisfactory for most of the assayed EDCs (>60%). Analysis of samples from four polluted areas of Douro River estuary and from two points of the Atlantic Ocean (Portugal) showed high amounts of E1 (up to 1.96 ng L−1), E2 (up to 14.36 ng L−1) and EE2 (up to 2.76 ng L−1). [ABSTRACT FROM AUTHOR]