Detection of emerging contaminants (UV filters, UV stabilizers and musks) in marine mussels from Portuguese coast by QuEChERS extraction and GC-MS/MS.

The UV filters and musk fragrances have come into focus because these compounds are contained and increasingly used not only in sunscreen products but also in many products of daily use, such as cosmetics, skin creams, plastics or varnish. In view of this, the main objective of the present work was to develop and validate a method for the determination of three UV filters, two UV stabilizers and four musks in mussel samples (Mytilus galloprovincialis). The procedure combined a QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) extraction method with an analysis by gas chromatography-tandem mass spectrometry (GC-MS/MS). The methodology allowed the determination of target analytes at trace concentration levels (ng/g), with mean recoveries ranging from 91 to 112%. A monitoring study was conducted in four beaches in the Portuguese coast which are impacted by recreational activities and outflow of treated waste water effluents in rivers. The results are used to assess the occurrence of UV filters in comparison with UV stabilizers and musk fragrances which indicate other activities than bathing.

Estrogen-like and dioxin-like organic contaminants in reclaimed wastewater: transfer to irrigated soil and groundwater.

In semi-arid regions, treated wastewater reuse for irrigation is a common practice since wastewater is considered as a non negligible water resource in these areas. However, treated wastewater contains traces of organic compounds which may contaminate the receiving environment i.e. soil and groundwater. Some of these organic compounds have the ability to bind to estrogen receptor (ER) or dioxin receptor (AhR, aryl hydrocarbon receptor). The fate of these compounds in effluent reused for irrigation, irrigated soils and groundwater is not well addressed yet. In the present study, estrogenic and dioxin-like activities were studied in three media: i) effluents reused for irrigation, ii) soils samples collected from the reclaimed water irrigated plot during six month irrigation, and iii) groundwater sampled before and after irrigation periods. Effluents reused for irrigation exhibited ER and AhR activities at 38.5 +/- 9.9 ng estradiol-equivalent/L (ng E2-EQ/L) and 113.3 +/- 27.7 ng dioxin-equivalent/L (ng TCDD-EQ/L), respectively. Soils showed ER activity (0.05 ng E2-EQ/g) only after 4 months of irrigation. AhR activities detected in all soil samples have not changed during irrigation. In groundwater, ER activities were detected in two piezometers indicating transfer of some estrogenic compounds.

Impact of urban wastewater discharges on the sediments of a small Mediterranean river and associated coastal environment: assessment of estrogenic and dioxin-like activities.

The Mediterranean region includes many small coastal rivers about which little is known concerning organic contaminant loads in their sediment. This study was designed to assess organic contamination in one of these small coastal rivers (Lez River) and associated coastal sediments. Levels of alkylphenols (APs), polycylic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs) were measured in sediments of the Lez River and two coastal lagoons impacted by wastewater discharges. In parallel, sediment surrounding a recently built submarine outfall that discharges treated wastewater, from an area encompassing some 450,000 inhabitants, into the sea was monitored a year after the beginning of emission via the outfall. Finally, these sediments were characterized by screening estrogenic, PAH-like and dioxin-like activities using in vitro bioassays. Both chemical analyses and bioassays revealed that wastewater inputs were a source of organic contamination of sediments from the Lez and lagoons, which still persisted 2 years after the discharges were stopped. APs could explain a small proportion of the overall estrogenic activities (up to 31%), suggesting that other estrogenic compounds were also present in the sediments. PAHs explained a great share (83% on average) of the EROD induction potency of the extracts. This survey should be the first step in the long-term monitoring of these sites.

Polycyclic aromatic hydrocarbon metabolites and 7-ethoxyresorufin O-deethylase activity in caged European eels.

This study investigated the contribution of two biomarkers, bile polycyclic aromatic hydrocarbon (PAH) metabolites and 7-ethoxyresorufin O-deethylase (EROD), activity in the assessment of PAH contaminated sites. European eels (Anguilla anguilla) were caged in a freshwater stream upstream and downstream from local industrial effluent outlets. Bile PAH metabolites were recorded as fluorescent aromatic compounds by synchronous fluorescence spectroscopy and as a marker for total PAH metabolism: 1-hydroxypyrene (1-OH Pyr) was isolated by high-pressure liquid chromatography and quantified. After 14 and 28 days of caging, EROD activity, bile fluorescence (synchronous fluorometric measurement), and 1-OH Pyr concentrations in bile were higher at the downstream site than at the upstream site. This increase was similar after 2 and 4 weeks of caging. During a reversibility study, EROD activity, bile fluorescence, and 1-OH Pyr concentrations decreased, and this trend was similar for the three markers. These results suggest that PAHs could be the main factor responsible for EROD induction in eels caged at the downstream site.

Estrogenic activity of cosmetic components in reporter cell lines: parabens, UV screens, and musks.

In this work, the estrogenic effects of three classes of substances included in cosmetic formulations-parabens, ultraviolet (UV) screens, and musk fragrances-were studied. Their estrogenic activity was measured with the use of three reporter cell lines: HELN, HELN ERalpha, and HELN ERbeta. These three cell lines allowed for the measurement of estrogenic activity toward estrogen receptors alpha and beta (ERalpha and ERbeta, while taking nonspecific interactions into account. Eight of the 15 substances tested showed specific estrogenic activity with the following degree of potency on ERalpha butylparaben > propylparaben > homosalate = octyl-dimethyl-PABA = 4-methyl-benzylidenecamphor = octyl-methoxycinnamate > ethylparaben = galaxolide. Among these active substances, parabens activated ERalpha and ERbeta similarly, UV screens activated ERalpha moderately and had almost no effect on ERbeta, and fragrances did not activate ERbeta. Methylparaben, ethylparaben, musk moskene, celestolide, and cashmeran did not activate estrogenic responses up to 10(-5) M. Musk ketone and benzophenone-3 were not considered estrogenic at 10(-5) M.

Estrogenic activity in water and sediments of a French river: contribution of alkylphenols.

Alkylphenols, known to possess estrogenic activity, have been found in the aquatic environment. In this study, we focused on the contribution of alkylphenols to total estrogenic activity in sediment and water extracts of French rivers. Four sites representing rural, agricultural, urban, and industrial watersheds were studied. The concentrations of alkylphenols in water and sediment were quantified by GC/MS. Estrogen-responsive reporter cell lines (MELN) have been used for investigating estrogenic activity at these sites. These observed activities were compared with activities mediated by known concentrations of alkylphenols. In water, the concentration of alkylphenols, from 0.06 to 0.550 microg x L(-1) and from < 0.001 microg x L(-1) to 0.077 microg x L(-1) for nonylphenols and 4t-octylphenol, respectively, were too low to contribute to the observed estrogenic activity. In sediment of the industrial, rural, and urban sites, the observed estrogenic activities could be explained in great part by the alkylphenol concentrations from 0.26 to 2.87 microg x g(-1) and from 0.005 microg x g(-1) to 0.49 microg x g(-1) for nonylphenols and 4t-octylphenol, respectively. In the agricultural site, the alkylphenols (0.022 microg x g(-1) of nonylphenols) poorly contribute to the observed estrogenic activity. Other compounds, such as natural and synthetic hormones, present in water and sediments could act additively in the overall activity.