Occurrence of organotin compounds in waters of the spanish coast under the European Water Framework Directive

Organotin compounds (OTCs), such as tributyltin (TBT), are persistent organic pollutants that are present in water samples (surface water, river water, sea water, waste water, etc.) because of anthropogenic activities (antifouling agents in ship paints, biocides in polymers, etc.). The toxicity and endocrine disruption potential of these chemicals have been demonstrated even at very low levels (<1 ng L−1) (Devos et al. 2012). Due to the extensive presence of OTCs in all environmental media as well as their adverse effects on human health and biota, quantitative and qualitative determination of those com-pounds in complex environmental matrices has become a matter of great concern, mainly butyl and phenyl-substituted. Also, these compounds are included in the list of priority substances according to the EU Directive 2013/39/EU amending Directives 2000/60/EC and 2008/105/EC as regards priority substances in the field of water policy. This directive specifies annual average environmental quality standard (AA-EQS) of 0.2 ng L−1 TBT and a maximum allowable environmental quality standard (MAC-EQS) of 1.5 ng L−1 TBT for all surface waters. Samples were collected in two semiconfined coastal areas, one of them an area with high industrial and port activities (Ría de Vigo) and the other one with high touristic and agricultural activity (Mar Menor).The sampling campaigns were performed in spring and autumn of 2015. The levels of MBT, DBT, TBT, MPhT, DPhT and TPhT in the seawater samples were analyzed by HS-SPME-GC–QqQMS/ MS method (Moscoso-Pérez et al. 2015). MPhT, DPhT and TPhT were not detected in any sample at levels higher than LOQ. For butylated compounds, MBT, DBT and TBT were detected in 100% of the analyzed samples in the Mar Menor. In the Vigo estuary, MBT has been detected in 83.3% of the samples, the DBT in 75% and the TBT in 88%. The TBT is present in 92% of the total of 39 analyzed samples, being detected in 100% of the samples of the Mar Menor and in 88% of the samples of the Ría de Vigo. These levels are similar than those detected in other locations, and lower than the detected in ports near the coast of Gijón characterized by a great maritime traffic (Centineo et al. 2004).Program of Consolidation and Structuring of Units of Competitive Investigation of the University System of Galicia (Xunta de Galicia) potentially cofinanced by ERDF in the frame of the operative Program of Galicia 2007-2013 (reference: GRC2013-047) and by the Ministry of Economy and Competitiveness (IMPACTA, project reference: CTM2013-48194-C3-2-R, and ARPA-ACUA, project reference: CTM2016-77945-C3-3-R)

No evidence that vitellogenin protein expression is induced in marine mussels after exposure to an estrogenic chemical

A wide variety of endocrine disrupting chemicals reach the marine environment and can cause harmful effects in different marine organisms. Vitellogenin (Vtg), the egg-yolk precursor, is a commonly used endocrine disruption biomarker in fish and more recently in marine invertebrates under the assumption of high expected similarities in the endocrine system of vertebrates and invertebrates. However, this assumption has been recently questioned. The results from previous studies focused on bivalve molluscs showed that Vtg induction could be misleading because of the use of either non-robust or indirect techniques to measure Vtg. In this study, mussels (Mytilus galloprovincialis) were exposed to either 10 or 100 ng/L of the synthetic hormone 17α-ethinylestradiol (EE2) at different exposure times (4 and 24 days) and under different feeding regimes (representing different energy balances), and Vtg levels in both male and female mussel gonads were quantified by label free shotgun LCMS/MS proteomic analysis. Vtg protein was not detected in male gonads. In female gonads, Vtg levels were not significantly affected by EE2 at any exposure time or EE2 concentration tested, whereas a significant correlation was found between the degree of maturation of the gonad and Vtg levels in females. Results obtained in the present study critically question the use of Vtg as a biomarker of endocrine disruption in marine mussels, and show that the degree of maturation of the gonad can be an important confounding factor in the attempts to evaluate estrogenic effects through Vtg measurement in mussel gonad

Bioaccumulation of PCB-153 and effects on molecular biomarkers acetylcholinesterase, glutathione-S-transferase and glutathione peroxidase in Mytilus galloprovincialis mussels

In this study, PCB-153 bioaccumulation kinetics and concentration-response experiments were performed employing wild Mytilus galloprovincialis mussels. In addition, the activity of three enzymatic biomarkers: glutathione S-transferase (GST), glutathione peroxidase (GPx) and acetylcholinesterase (AChE), were measured in the mussel gills. The experimental data fitted well to an asymptotic accumulation model with a high bioconcentration factor (BCF) of 9324 L Kg-1 and a very limited depuration capacity, described by a low excretion rate coefficient (Kd = 0.083 d-1). This study reports by first time in mussels significant inhibition of GST activity and significant induction of GPx activity as a result of exposure to dissolved PCB-153. In contrast, AChE activity was unaffected at all concentrations and exposure times tested. The effects on both enzymes are time-dependent, which stresses the difficulties inherent to the use of these biomarkers in chemical pollution monitoring programs.Versión del editor3,746

PAHs, pesticides, personal care products and plastic additives in plastic debris from Spanish Mediterranean beaches

In this study the role of plastic debris as a pollution vector has been evaluated by determining the concentrations of hydrophobic organic contaminants in polymers from three Western Mediterranean coastal areas as well as their potential transfer to seawater. Plastic debris was sampled at three Iberian Peninsula Southeastern beaches, each affected by different predominant anthropogenic activities (tourism, agriculture, urban activities, transport and industry). Plastic debris was characterized by attenuated total reflection Fourier-transform infrared spectrometry. The organic contaminants were extracted from plastics by ultrasonic extraction with methanol and quantified by stir bar sorptive extraction coupled to gas chromatography–mass spectrometry (GC–MS). In two areas, the desorption of these contaminants from plastic debris to seawater during 24 h was also evaluated. The contaminant groups considered in this study (polycyclic aromatic hydrocarbons (PAHs), personal care products (PCPs), current use pesticides (CUPs), organochlorinated compounds (OCPs, including polychlorinated biphenyls and organochlorinated pesticides) and plastic additives were found in polymers from the three areas. The most abundant contaminants were plastic additives and PCPs, underlining the relevance of the leaching of plastic components, and urban and tourism activities as typical pollution sources in the coastal areas. In general, large piece-to-piece variability was found for all polymers and areas mainly as a consequence of their different origin, exposition time, use and surface-to-volume ratio. This fact difficulted the visualization of significant differences between polymers or areas, but for CUPs, whose concentrations were significantly higher in Cape Cope than in the other areas due to the influence of close agricultural activities. PCPs and CUPs were desorbed partially in seawater for 24 h, particularly the most hydrophilic compounds such as triazines and other CUPs. However, a significant fraction of other contaminants (mainly PAHs) was retained, which suggests they can be transported far away from their origin

Identification of contaminants of emerging concern with potential environmental risk in Spanish continental shelf sediments

The distribution of per- and polyfluoroalkyl substances (PFAS), alkylphenols, organotin compounds, phthalates, alkylated polycyclic aromatic hydrocarbons, current-use pesticides (CUPs) and personal care products (PCPs) was characterized in 29 surface sediments from two Spanish Iberian continental shelf areas (14 on the Atlantic and 15 on the Mediterranean coasts). Concretely, 115 organic contaminants were determined and a specific methodology was used for each contaminant group, including contaminants of emerging concern (CECs) and traditional ones, such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorinated pesticides (OCPs). PAHs, alkylated PAHs, alkylphenols and phthalates were found in all samples, showing mean concentrations per group higher than 20 ng/g (16–4974 ng/g d.w.) in the subregions under consideration (Galician, Cantabrian, Levantine-Balearic and Strait-Alboran). CUPs and PCPs were found in the majority of samples at very low concentrations of ng/g (1.4–46.8 ng/g d.w.), whereas organotins and PFAS were found principally in sediments from the Mediterranean subregions (2.5–3.9 ng/g d.w.). Different distribution patterns were observed for the contaminant groups and subregions under consideration as a consequence of the diverse predominant sources (industrial, urban, transport and agricultural activities) and environmental behavior (mainly hydrophobicity and persistence). Risk assessment confirmed the impact of phthalates, alkylphenols, PAHs and PCBs on Atlantic ecosystems and of alkylphenols, chlorpyrifos, phthalates, TBT, PAHs, OCPs and PCBs on the Mediterranean ones. Furthermore, the presence of CUPs, PCPs and PFAS in sediments from the Spanish continental shelf located between 2 and 31 km from the coast suggested that those contaminants may also provoke adverse effects on coastal marine ecosystems between their sources and their depositional areas