Distribution of endocrine disruptors in the Mondego River estuary, Portugal.

Recent studies in the Mondego River estuary demonstrated signs of pollution in the area, but the nature of the contamination remains unexplored. Because there seems to be any studies in that zone checking for the simultaneous presence of xenoestrogenic endocrine disrupting compounds, either of animal (estradiol and estrone), vegetal (daidzein, genistein and biochanin A), pharmaceutical (17alpha-ethynylestradiol) or industrial (bisphenol A, 4-octylphenol, 4-nonylphenol) origins, the main objective of this study was to investigate their presence, in every year season and at eight points along the estuarine gradient. For this propose, water samples (2 L) were collected in high and low tides, preconcentrated in the Oasis HLB cartridges and cleaned in silica cartridges before their analysis by HPLC-DAD and GC-MS. The current data showed the absence of contamination by animal or pharmaceutical estrogens and by alkylphenols, but demonstrated the presence of high levels of phytoestrogens (up to 1.1 mug/L) and of bisphenol A (up to 880.0 ng/L). Because these two chemicals existed in high environmental concentrations in the most upstream sampling station, and taking in account that these pollutants may additively contribute to endocrine disruption, namely on fish, it was concluded that at least this particularly area of the Mondego estuary deserves continuous monitoring programmes.

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 (17alpha-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.