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)

Compuestos orgánicos en aguas del estuario del Río Miño. Proyecto "TEAM-Miño"

Comunicación presentada al II Congreso Internacional de Ingeniería Civil y Territorio. Agua, Cultura y Sociedad. Vigo, 20 y 21 de Mayo de 2013.Los resultados de este trabajo se engloban en el Marco del proyecto TEAM-Miño “Transferencia de herramientas para la Evaluación, Ordenación, Gestión y Educación Ambiental en Estuarios” financiado por la Unión Europea (POCTEP 2007-2013), que pretende desarrollar herramientas comunes para la tipificación y clasificación del estado ecológico de las masas de agua de transición del sur de Galicia y norte de Portugal, con la finalidad de colaborar en la implantación de la Directiva Marco del Agua. Se han analizado 19 muestras de agua recogidas a lo largo del río Miño y sus afluentes. En ellas se han determinado diferentes contaminantes de amplio interés industrial y ambiental, como hidrocarburos aromáticos policíclicos (HAP), compuestos organoestánnicos, alquilfenoles y bisfenol A. Salvo excepciones, los niveles encontrados en las muestras no son elevados (<0,1 μg/L). La mayoría de los HAPs se encuentran por debajo de los límites de cuantificación del método analítico (MQL), siendo el compuesto mayoritario el naftaleno. Los compuestos organoestánnicos tampoco han sido detectados. Los alquilfenoles están presentes en todos los puntos muestreados (<MQL-1 μg/L), mientras que el bisfenol A se ha encontrado únicamente en dos de ellos, pero a altas concentraciones (>3 μg/L). En ningún caso las concentraciones medidas superan los límites establecidos en la Directiva 2008/105/CE

Occurrence, distribution and bioaccumulation of endocrine disrupting compounds in water, sediment and biota samples from a European river basin

The occurrence, distribution and bioaccumulation of five endocrine disrupting compounds (4-tert-octylphenol, 4-n-octylphenol, 4-n-nonylphenol, nonylphenol and bisphenol A) in water, sediment and biota (Corbicula fluminea) collected along the Minho River estuary (NW Iberian Peninsula) were examined. Samples were collected in two campaigns(May andNovember, 2012) and analyzed by different extraction procedures followed by liquid chromatography tandem mass spectrometry determination. The presence of linear isomers (4-noctylphenol and 4-n-nonylphenol) was scarcely observed whereas branched isomers (4-tert-octylphenol and nonylphenol) were measured in almost all samples.Wastewater treatment plant effluents and nautical, fishing and agricultural activities are considered the primary source of pollution of the river by alkylphenols. The presence of bisphenol A in the river could be mainly associated to punctual sources of contamination from industrial discharges. A decrease in the total concentration of phenolic compounds in water was observed from spring to autumn (from 0.888 μg L−1 in May to 0.05 μg L−1 in November), while similar values were shown in C. fluminea samples from the two campaigns (1388 and 1228 ng g−1 dw in spring and autumn, respectively). In sediments, the total concentration of the target compounds varied between 13 and 4536 ng g−1 dw (average of 1041 ng g−1 dw). Sediment–water partition coefficient (Kd), bioaccumulation factor (BAF) and biota–sediment accumulation factor (BSAF) were estimated and highest values were obtained for nonylphenol. Calculated risk quotients showed low and moderate risk for the aquatic environment from the presence of the target compounds at all sampling points. The estimation of the daily intake of the studied compounds via water and biota ingestion indicated no risk for human health.Versión del editor3,258

Bioaccumulation of 4-nonylphenol and effects on molecular biomarkers, acetylcholinesterase, glutathione-S-transferase and glutathione peroxidase in Mytilus galloprovincialis mussel gills

Wild marine mussels, Mytilus galloprovincialis showed a moderate bioaccumulation ability when exposed to waterborne 4-nonylphenol (4-NP), with a bioconcentration factor (BCF) of 6850 L Kg 1 (dry weight). Kinetic and concentration-response experiments were performed and three enzymatic biomarkers in mussel gills were measured: Glutathione S-transferase (GST), glutathione peroxidase (GPx) and acetylcholinesterase (AChE). Exposure of mussels to environmentally relevant concentrations (25 e100 mg L 1) of 4-nonylphenol significantly inhibited the AChE activity and induced the GST and GPx activities. GST induction was dose dependent whilst GPx activity showed a less consistent pattern, but in both cases the induction remained after a 10 d depuration period. Mussels seem capable of eliminating 4- NP from their tissues through a mechanism involving GST inductionVersión del edito

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

Occurrence of endocrine disrupting compounds in five estuaries of the northwest coast of Spain: Ecological and human health impact

The occurrence and spatial distribution of alkylphenols (4-tert-octylphenol, 4-n-octylphenol, 4-n-nonylphenol, nonylphenol) and bisphenol A were examined in five estuaries along the Northwest coastal area of Spain. As far as we know, no previous works about this topic could be found in the literature. A total of 98 seawater samples were collected during May 2011–July 2012 and analyzed by a highly sensitive DLLME–LC–MS/MS methodology recently developed. Results indicated nonylphenol was the most ubiquitous compound with maximal concentration of 0.337 μg L−1 (Ría de Vigo). The environmental quality standards (EQS) established in Directive 2013/39/EU for 4-tert-octylphenol were slightly exceeded in some sampling points. Fishing harbours, water treatment plant and industrial discharges were supposed as the main sources of contamination. Low and medium ecological risk was determined in all estuaries. Possible endocrine effects on biota and population were estimated in terms of estrogenic activity and daily intake respectively, and no risk was found in any case.En prensa3,206

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