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The scarcity of the most widely used species for assessing marine pollution (mussels) in some areas brings out the need to test the use of a different organism. In this study, 11 sampling sites along the Atlantic Spanish coast were selected and both mussels (Mytilus galloprovincialis) and limpets (Patella sp.) were analysed for PAHs, PBDEs and PCBs. The concentrations of the different pollutants in both species followed the same general distribution allowing us to differentiate polluted and unpolluted sites using any of them. Although the concentrations found in limpets were generally lower than those measured in mussels, a good correlation was observed for most of the groups of pollutants and also for every individual congener. A conversion factor was proposed for most of the individual PAH and PCB congeners, allowing the conversion of limpet concentration into mussel concentration that can be directly applied in assessments using environmental criteria derived for mussels., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The northwest coast of Spain is characterized by an irregular coastline rich in marine life and with the highest mussel production in Europe. Taking this into account, the characterization of the pollution levels and the sources involved appear necessary. Not only were parent Polycyclic Aromatic Hydrocarbons (PAHs) analysed but also their alkylated homologues. In total, 35 compounds were analyzed in 5 sediment cores. Sediments were collected using a box core dredge and extracted by (Pressurized Liquid Extraction) whilst the quantification of PAHs was performed using gas chromatography coupled to mass spectrometry (GC-MS). The total concentration detected varied from 49.6 to 2489 ng g -1 dry weight (d.w.) of which parent PAHs ranged from 44.5 to 2254 ng g -1 d.w. and alkylated PAHs varied from 5.04 to 317 ng g -1 d.w. Temporal and spatial evolution were outlined and pollution sources were identified along with a possible correlation between this pollution and local history and industry. Most of the PAHs from the superficial samples have a biomass and coal combustion profile, and some specific, localized events are reflected in the total PAH concentration evolution. Moreover, the study of the deepest layers of the sampled cores provides a baseline to develop background concentration values that will help in future sediment quality assessment.

Biomarkers are useful tools to assess biological effects of pollutants and have been extensively used in monitoring programs to determine ecosystem health. In these programs, a wide range of environmental conditions are covered and sometimes, obtained data are difficult to interpret because of natural variables are affecting biomarker responses. Among these variables, musseĺs reproductive status has been considered one of the most changing variables between sites in a monitoring survey. Thus, the main aim of this work was to identify the effect that mussel reproductive status has on biomarker responses. For that purpose, mussels sampled at two periods in the reproductive cycle (reproductive and resting stages) were conditioned to the same laboratory conditions and exposed to fluoranthene (FLU) for three weeks. Studied biomarkers covering a wide range of organism responses were included: bioaccumulation, physiological rates (clearance rate -CR-, absorption efficiency -AE-, respiration rate -RR- and their integration in the scope for growth -SFG-), antioxidant enzyme activities (superoxide-dismutase -SOD-, catalase -CAT-, glutathione reductase -GR-, glutathione peroxidase -GPx-, glutathione-S-tranferase -GST-) and biochemical damage responses (lipid membrane peroxidation -LPO-). The results obtained evidenced that the levels of the biomarkers studied (RR, SOD, CAT and GPx) were higher at reproductive than at resting stage. On the other hand, the effect of toxicant was observed in SFG, CAT and GPx but this effect was only detected during the resting period. Moreover, there was a deterioration of mussel gonadal tissue with FLU exposure during reproductive stage. FLU accumulation in mussel tissues was also dependent of the reproductive status with higher internal concentrations during resting than reproductive period. In conclusion, there was a strong effect of reproductive status on studied biomarkers which seems to mask the effect of FLU at reproductive stage. The present study evidences the need to include the measurement of mussel biological status in marine pollution monitoring programs for a correct interpretation of biomarker data., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Wild mussels (Mytilus galloprovincialis) were selected as bioindicators of chemical pollution to evaluate the occurrence and spatial distribution of five endocrine disrupting compounds in the Spanish Atlantic coast and Bay of Biscay. A total of 24 samples were collected in May, 2011 and analysed by selective pressurized liquid extraction followed by liquid chromatography tandem mass spectrometry determination. Branched alkylphenols (4-tert-octylphenol and nonylphenol) were determined in more than 90% of the analysed samples whereas the presence of linear alkylphenols (4-n-octylphenol and 4-n-nonylphenol) was scarcely detected (<12% of the samples). Wastewater treatment plants discharges and nautical, fishing and shipping activities were considered the primary sources of contamination by alkylphenols. Bisphenol A was found in 16% of the analysed samples associated to punctual industrial discharges. A total endocrine disrupting compound (alkylphenols and bisphenol A) average concentration of 604ngg(-1) dw was calculated and nonylphenol was the main contributor in almost all sampling points., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Biomarkers have been extensively used in monitoring programs with the aim of assessing the biological effects of pollutants on marine organisms and determining environmental status. Data obtained from these programs are sometimes difficult to interpret due to the large amount of natural variables affecting biological processes, which could act as confounding factors on biomarker responses. The main aim of this work was to identify the effect of one of these variables, the food availability, and consequently, the mussel nutritive status, on biomarker responses. For that purpose, mussels (Mytilus galloprovincialis) were conditioned to three different food rations for 2 months in order to create three mussel nutritive statuses and afterwards, each status was exposed to three nominal concentrations of fluoranthene (FLU) for 3 weeks. A battery of biomarkers was considered in this study to cover a wide range of organism responses, both physiological (scope for growth - SFG) and biochemical (superoxide dismutase - SOD, catalase - CAT, glutathione reductase - GR, glutathione peroxidase - GPx, glutathione-S-transferase - GST and phenoloxidase - PO activities, and lipid membrane peroxidation - LPO). The results obtained, evidenced that most of the studied biomarkers (SFG, SOD, CAT, GPx, and PO) were strongly affected by mussel nutritive status, showing higher values at lower status, whereas the effect of toxicant was not always evident, masked by the nutritive status effect. This paper demonstrates that toxicants are not the only source of variability modulating pollution biomarkers, and confirms nutritive status as a major factor altering biochemical and physiological biomarkers., (Copyright © 2015 Elsevier B.V. All rights reserved.)

The aim of this note is to discuss the relevance of the interaction/integration of monitoring of contaminants for the protection of the marine environment and for human health safety (descriptors 8 and 9, respectively) within the Marine Strategy Framework Directive (MSFD). The identification of possible relations between contaminant levels in sediments and tissues of fish and other seafood, as well as the association of those levels to pollution sources, are major challenges for marine researchers. The Spanish initial assessment in the North-East Atlantic marine region was used as an example to show some gaps and loopholes when dealing with the relationship between descriptors 8 and 9. The main problem to deal with is that monitoring programmes intended for the assessment of marine environmental quality and for human health safety usually apply different approaches and methodologies, and even different tissues are analysed in some species (mainly fish). It is therefore recommended to make a profound revision of current sampling strategies, procedures and methodologies, including the selection of target species and tissues and to improve the traceability of samples of fish and other seafood for human consumption. On the other hand, despite the scope of descriptor 9 which is limited to commercially relevant species, this fact should not be an obstacle in the application of the 'ecosystem approach' within the MSFD. In order to appropriately solve these shortcomings, an information exchange system between authorities dealing with descriptors 8 and 9 should be strongly encouraged for the next steps of the MSFD's implementation.

This study undertakes an overall assessment of pollution in a large region (over 2500 km of coastline) of the N-NW Spanish coast, by combining the use of biochemical (AChE, GST, GPx) and physiological (SFG) responses to pollution, with chemical analyses in wild mussel populations (Mytilus galloprovincialis). The application of chemical analysis and biological techniques identified polluted sites and quantified the level of toxicity. High levels of pollutants were found in mussel populations located close to major cities and industrialized areas and, in general, average concentrations were higher in the Cantabrian than in the Iberian Atlantic coast. AChE activities ranged between 5.8 and 27.1 nmol/min/mg prot, showing inhibition in 12 sampling sites, according to available ecotoxicological criteria. GST activities ranged between 29.5 and 112.7 nmol/min/mg prot, and extreme variability was observed in GPx, showing activities between 2.6 and 64.5 nmol/min/mg prot. Regarding SFG, only 5 sites showed 'moderate stress' (SFG value below 20 J/g/h), and most sites presented a 'high potential growth' (>35 J/g/h) corresponding to a 'healthy state'. Multivariate statistical techniques applied to the chemical and biological data identified PCBs, organochlorine pesticides and BDEs as the main responsible of the observed toxicity. However, the alteration of biological responses caused by pollutants seems to be, in general, masked by biological variables, namely age and mussel condition, which have an effect on the mussels' response to pollutant exposure., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Oil and chemical spills in the marine environment are an issue of growing concern. Oil exploration and exploitation is moving from the continental shelf to deeper waters, and to northern latitudes where the risk of an oil spill is potentially greater and may affect pristine ecosystems. Moreover, a growing number of chemical products are transported by sea and maritime incidents of hazardous and noxious substances (HNS) are expected to increase. Consequently, it seems timely to review all of the experience gained from past spills to be able to cope with appropriate response and mitigation strategies to combat future incidents. Accordingly, this overview is focused on the dissemination of the most successful approaches to both detect and assess accidental releases using chemical as well as biological approaches for spills of either oil or HNS in the marine environment. Aerial surveillance, sampling techniques for water, suspended particles, sediments and biota are reviewed. Early warning bioassays and biomarkers to assess spills are also presented. Finally, research needs and gaps in knowledge are discussed., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

The aim of this study was to establish the temporal trends and spatial distribution of Polycyclic Aromatic Hydrocarbons (PAHs) in Ria de Vigo by means of studying the PAH burden in wild mussels. The samples were collected in eight sites along the margins of the Ria de Vigo during November from 1998 to 2008 and Polycyclic Aromatic Hydrocarbon contents were determined using high performance liquid chromatography-fluorescence derivatization (HPLC-FLD). Quality of chemical analysis was guaranteed by participation in QUASIMEME intercalibration exercises carried out during the period of analysis. The concentrations for the sum of 13 PAHs were in the range 24-480 μg/kg dw, typical of an urban and industrialized area (50-500 μg/kg dw) except for a punctual input in La Guía in 1998 that led to a concentration above 1,000 μg/kg dw. In general, the sites in the outermost section of the estuary (ría) showed the lowest values, with an increasing gradient in the medium and inner parts of the ría. Temporal patterns show, in general, a downward trend. The relative proportion of 3 and 4 ring PAHs also varies with the site, the former being predominant in the outermost area and the latter in the medium and inner parts of the ría. This is consistently related with the sources and processes taking place in different areas of the estuary.

To establish the connection between pollutant levels and their harmful effects on living resources, coastal monitoring programmes have incorporated biological tools, such as the scope for growth (SFG) in marine mussels and benthic macrofauna community indices. Although the relation between oxygen-depleting anthropogenic inputs and the alteration of benthic communities is well described, the effects of chemical pollutants are unknown because they are not expected to favour any particular taxa. In this study, the combined efforts of five research teams involved in the investigative monitoring of marine pollution allowed the generation of a multiyear data set for Ría de Vigo (NW Iberian Peninsula). Multivariate analysis of these data allowed the identification of the chemical-matrix combinations responsible for most of the variability among sites and the construction of a chemical pollution index (CPI) that significantly (P < 0.01) correlated with biological effects at both the individual and the community levels. We report a consistent reduction in the physiological fitness of local populations of mussels as chemical pollution increases. The energy balance was more sensitive to pollution than individual physiological rates, but the reduction in the SFG was primarily due to significantly decreased clearance rates. We also found a decrease in benthic macrofauna diversity as chemical pollution increases. This diversity reduction resulted not from altered evenness, as the classic paradigm might suggest, but from a loss of species richness.

The distribution of polycyclic aromatic hydrocarbons was determined in surface sediments collected at 36 stations along the Spanish Northern continental shelf in March and September 2003, and February 2005. Concentrations of PAHs (Sigma13 parent components) were in the range of 22-47528 mug/kg dw, the highest values corresponding to coastal urban-industrial hotspots and decreasing offshore. Sediment quality guidelines (SQGs) showed that concentrations of total PAHs were below the threshold effect level (TEC) in 27 stations (81%) and above in 7, two of which (Gijon and Bilbao) were above the probable effect concentration (PEC). The detailed study of diagnostic ratios suggested a rather uniform mixture of petrogenic and pyrolytic PAH sources along the continental shelf, with a slight decrease of the latter moving westwards and offshore. In order to assess the incidence of sediment sampling on the variability of the results, selected stations were also monitored in February and September 2004 and September 2005. The average field variance of the values obtained for each station was 31% that decreased to 23% when the values were normalized to TOC., (Copyright 2009 Elsevier Ltd. All rights reserved.)

The aim of this study was to assess environmental quality at some of the sites most severely affected by the Prestige oil spill off 2 years after the spillage (April and November 2004). For this purpose analyses of polycyclic aromatic hydrocarbons (PAH) and several biochemical (antioxidant enzymes catalase, glutathione reductase, glutathione peroxidase, superoxide dismutase and DT-diaphorase and lipid peroxidation) and physiological [scope for growth (SFG)] biomarkers were determined on wild mussel populations (Mytilus galloprovincialis) collected at four points along the Costa da Morte and compared with those of a reference site not affected by the oil spill. Results showed that PAH contents had markedly decreased 17 months after the accident, although they were higher in April than in November, when they showed values similar to background levels reported for this area. Nevertheless, the predominance of chrysene on PAH profiles, similarly to findings obtained immediately after the spill, indicated the Prestige as their main source. In spite of the low PAH levels recorded, antioxidant activity levels (explained through the integrated antioxidant response-IAR) were higher in the Costa da Morte than at the reference site either in April and November. In April IAR seems to be related to PAH levels found 3 months after the accident (February 2003), suggesting the persistence in the environment of oxidative stress-producing components from the spill. However, evidence of oxidative stress was not reflected at physiological level by scope for growth, with only very slight differences being observed between values from the reference site and those from Costa da Morte sites. In conclusion, although 2 years after the spill PAHs bioaccumulated by mussels from the Costa da Morte had decreased to background levels, biochemical parameters showed signals of oxidative stress in mussels from this area. However, SFG reflected a good health status for the mussel populations studied and did not reveal evidence of physiological disturbance either 17 or 24 months after the Prestige spill.

Polycyclic aromatic hydrocarbons (PAHs) were determined in tissues of wild mussels (Mytilus galloprovincialis) from the Galicia coast (NW Spain) in order to assess the extent of the environmental impact caused by the Prestige oil spill (November 13, 2002). Three sampling campaigns were carried out in February, June and November 2003 at 24 stations along the Galicia coast, from La Guardia (Pontevedra) to Ribadeo (Lugo). The spatial distribution of PAHs found in the first sampling period, clearly revealed the central area (Costa da Morte) as the most affected by the oil spill. In these stations, concentrations up to 7780 microg/kg dw of the sum of 13 parent PAHs were found 2-3 months after the spill. Molecular parameters within the aliphatic and aromatic fractions confirmed the presence of the Prestige oil in these samples. The levels markedly decreased at most of the stations in the second sampling and recovered to levels found before the spill in November 2003, 1 year after the accident (29-279 microg/kg dw, av. 133+/-83 microg/kg dw). However, a certain increase was observed in some sites which could be related to the remobilization of oil residues from still unclean intertidal spots or sediments due to the winter marine weather conditions.