Os ftalatos e alquilfenóis são grupos de substâncias classificadas como interferentes endócrinos (IE) por órgãos internacionais, portanto a presença destes nas diversas matrizes ambientais é preocupante, visto que mesmo em concentrações muito baixas são capazes de alterar o funcionamento normal de um organismo podendo causar anomalias no sistema reprodutor animal, câncer, obesidade, infertilidade, entre outros. No Brasil, há poucos estudos sobre a ocorrência e comportamento de ftalatos e alquilfenóis no meio ambiente. Desta forma, o objetivo desse trabalho foi estudar a presença do dimetil ftalato (DMP), dietil ftalato (DEP), dibutil ftalato (DBP), benzilbutil ftalato (BBP), bis(2-etil-hexil) ftalato (DEHP), di-n-octil ftalato (DnOP), 4-octilfenol (4-OP), 4-terc-octilfenol (4-t-OP) e 4-nonilfenol (4-NP) em água bruta e potável provenientes do rio Guandu, localizado no Estado do Rio de Janeiro, Brasil, e avaliar seus potenciais estrogênicos. Para isto, entre março e dezembro de 2015, foram realizadas 6 coletas: de água bruta, do rio Guandu, nos municípios de Nova Iguaçu e Japeri, e de água potável, em Nova Iguaçu, próximo à estação de tratamento de água da região. Uma metodologia analítica foi desenvolvida utilizando extração em fase sólida combinada à cromatografia gasosa de alta resolução acoplada à espectrometria de massas em modo seletivo de íons (EFS-CGAR-EM-MSI) para a separação e determinação simultânea dos IE estudados. O menor limite de detecção (LD) do método foi de 3,6 μg.L-1, para o DMP e o maior LD foi de 51,7 μg.L-1, para o DnOP. As curvas dos padrões sintéticos obedeceram aos critérios do INMETRO, apresentando boa linearidade, com r > 0,90. O DEHP foi o que apresentou maior concentração em todas as amostras, sendo que em 50% das amostras de água bruta e em 40% das amostras de água potável essa substância foi encontrada em níveis de concentrações superiores a 1000 ng.L-1. O 4-t-OP variou de 0,05 a 0,97 μg.L-1 e de 0,13 a 0,27 μg.L-1, nas amostras de água bruta e potável, respectivamente. Essas concentrações excedem o valor determinado pela Final European Union 2455/2001/EC, que estabelece um limite de 0,01 μg.L-1 dos isômeros de octilfenóis em águas superficiais. Foi aplicado o ensaio in vitro Yeast Estrogen Screen (YES) para a determinação da atividade estrogênica das soluções dos padrões sintéticos e das amostras, onde somente o DMP e o 4-t-OP apresentaram estrogenicidade e uma curva sigmoidal semelhante à do 17β-estradiol, enquanto que o BBP, 4-OP e 4-NP apresentaram pouca resposta estrogênica nas faixas de concentração analisadas. 75% das amostras de água bruta do rio Guandu analisadas apresentaram atividade estrogênica e o valor do EQ-E2 máximo encontrado foi de 31,9 ng.L-1, o que é preocupante, visto que concentrações superiores a 1 ng.L-1 podem causar riscos à saúde de seres humanos e animais. Com base nos resultados avaliados, pode-se concluir que o método analítico desenvolvido e sua aplicação foi uma importante contribuição para o estudo de IE em águas do rio Guandu

Background, aim and scope Ria de Aveiro (Portugal) is a shallow coastal lagoon of high economic and ecological importance. Hardly any data on its chemical pollution by polar organic pollutants are available in literature. This study focused on the presence and sources of a series of phenolic endocrine-disrupting compounds (EDCs) in this area, including parabens, alkylphenolic compounds and bisphenol-A (BPA). A number of possible sources of pollution are present in the area, including the large harbours present in the lagoon, the city of Aveiro and the rivers discharging into the area. A recently constructed submarine wastewater outfall, located a few kilometres from the lagoon inlet has also been suggested as a possible source of pollution to Ria de Aveiro in several publications. The aim of the current field study was to investigate the occurrence and main sources of phenolic endocrine disruptors in Ria de Aveiro. Materials and methods An extensive sampling campaign was performed, with surface water and wastewater grab samples taken at over 50 locations, in duplicate on different days. Samples were treated using solid phase extraction and analysed by liquid chromatography tandem mass spectrometry. Results and discussion Concentrations in lagoon water were generally low: not exceeding 20 ng/L for most analytes. Levels in river water exceeded those in the lagoon by a factor 3 to 500 (o-phenylphenol (PhP) and nonylphenoxy ethoxy acetic acids (A9PEC), respectively), with concentrations up to 700 ng/L for BPA and 7,300 ng/L for A9PEC. Samples from the harbours showed EDC levels similar to those in the rest of the lagoon, but in the city of Aveiro, elevated concentrations were observed for alkylphenol ethoxylates (A9PEO), A9PEC, PhP and BPA. Wastewater effluents showed low levels for parabens, whilst alkylphenolic compounds reached several micrograms per litre. The effluents are discharged into the ocean via a submarine outfall, but as marine water near the outfall showed slightly elevated concentrations only for A9PEO, it does not seem to be a significant source of these EDCs for the area. Conclusions All the studied phenolic EDCs were detected in the study area, with high levels found in some of the rivers discharging into the lagoon, and generally low concentrations in the lagoon itself. The main sources for all investigated EDCs were the rivers Caster and Antuã which discharge into the lagoon. The city of Aveiro was identified as a secondary source. As the tidal water exchange volume is much larger than the freshwater input from the rivers, concentrations of phenolic EDCs remained low in the lagoon.

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−1–μg L−1). Thus to conclude about the influx of EDCs in the lagoon, water samples were taken every 2 months, during 1 year (2010), in low tide at nine sites distributed along the coastline. Water samples (1 L) were preconcentrated in the Oasis HLB cartridges and cleaned in silica cartridges before their analysis by GC-MS. Data showed the ubiquitous presence of potentially hazardous amounts of estrogens (particularly of ethynylestradiol, up to 24.3 ng L−1), nonylphenol (up to 547 ng L−1), and sitosterol (up to 12,300 ng L−1), 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.

Comprehensive two-dimensional gas chromatography has been successfully applied to the analysis of various organic contaminants; however, few studies report its use in the analysis of endocrine disrupting compounds. These compounds are suspected to cause dysfunction of the endocrine system in humans and animals. This work describes the development of a method to analyse dibutylphthalate, benzylbutylphthalate, nonylphenol and octylphenol in water using solid-phase microextraction (SPME) and comprehensive two-dimensional gas chromatography with a flame ionisation detector. The merit parameters of the comprehensive two-dimensional gas chromatography with flame ionisation detector method were weighed against a gas chromatography/mass spectrometry-single ion monitoring method of endocrine disrupting compounds analysis. The compounds were evaluated over a concentration range of 0.2 to 6.0 mu g L-1. The use of a two-dimensional chromatography method proved to be advantageous in analysing endocrine disrupting compounds, according to the observed increase of the signal relative to the noise and peak resolution.

The aquaculture industry is an expanding activity, mainly due to the world population demand of fish. However, intensive production and the use of chemicals have raised environmental concerns and have questioned the quality of cultured fish in comparison to wild fish. Up to date, there is little information regarding pollutant residues in cultured stocks and the risks associated to consumption. Here we summarize recent data on pollutants exposure, together with biochemical responses in both cultured and wild sea bass (Dicentrarchus labrax) from the Iberian Peninsula. The obtained data highlights the use of chemicals in current aquaculture practices as a significant source of pollution in cultured fish that poses a risk to exposed individuals and may negatively impact aquatic ecosystems. Nonetheless, a controlled use of those chemicals and a careful selection of the aquaculture location can ensure relatively low and homogeneous levels of pollutants in cultured fish in comparison to wild specimens.