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Shipping industry and seaborne trade have rapidly increased over the last fifty years, mainly due to the continuous increasing demand for chemicals and fuels. Consequently, despite current regulations, the occurrence of accidental spills poses an important risk. Hazardous and noxious substances (HNSs) have been raising major concern among environmental managers and scientific community for their heterogeneity, hazardous potential towards aquatic organisms and associated social-economic impacts. A literature review on ecotoxicological hazards to aquatic organisms was conducted for seven HNSs: acrylonitrile, n-butyl acrylate, cyclohexylbenzene, hexane, isononanol, trichloroethylene and xylene. Information on the mechanisms of action of the selected HNS was also reviewed. The main purpose was to identify: i) knowledge gaps in need of being addressed in future research; and ii) a set of possible biomarkers suitable for ecotoxicological assessment and monitoring in both estuarine and marine systems. Main gaps found concern the scarcity of information available on ecotoxicological effects of HNS towards marine species and their poorly understood mode of action in wildlife. Differences were found between the sensitivity of freshwater and seawater organisms, so endpoints produced in the former may not be straightforwardly employed in evaluations for the marine environment. The relationship between sub-individual effects and higher level detrimental alterations (e.g. behavioural, morphological, reproductive effects and mortality) are not fully understood. In this context, a set of biomarkers associated to neurotoxicity, detoxification and anti-oxidant defences is suggested as potential indicators of toxic exposure/effects of HNS in marine organisms. Overall, to support the development of contingency plans and the establishment of environmental safety thresholds, it will be necessary to undertake targeted research on HNS ecotoxicity in the marine environment. Research should address these issues under more realistic exposure scenarios reflecting the prevailing spatial and temporal variability in ecological and environmental conditions., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Among organic pollutants existing in coastal areas, polycyclic aromatic hydrocarbons (PAHs) are of great concern due to their ubiquity and carcinogenic potential. The aim of this study was to evaluate the seasonal patterns of PAHs in the digestive gland and arm of the common octopus (Octopus vulgaris) from the Northwest Atlantic Portuguese coast. In the different seasons, 18 PAHs were determined and the detoxification capacity of the species was evaluated. Ethoxyresorufin O-deethylase (EROD) and ethoxycoumarin O-deethylase (ECOD) activities were measured to assess phase I biotransformation capacity. Individual PAH ratios were used for major source (pyrolytic/petrogenic) analysis. Risks for human consumption were determined by the total toxicity equivalence approach. Generally, low levels of PAHs were detected in the digestive gland and in the arm of octopus, with a predominance of low molecular over high molecular weight compounds. PAHs exhibited seasonality in the concentrations detected and in their main emission sources. In the digestive gland, the highest total PAH levels were observed in autumn possibly related to fat availability in the ecosystem and food intake. The lack of PAH elimination observed in the digestive gland after captivity could be possibly associated to a low biotransformation capacity, consistent with the negligible/undetected levels of EROD and ECOD activity in the different seasons. The emission sources of PAHs found in the digestive gland varied from a petrogenic profile observed in winter to a pyrolytic pattern in spring. In the arm, the highest PAH contents were observed in June; nevertheless, levels were always below the regulatory limits established for food consumption. The carcinogenic potential calculated for all the sampling periods in the arm were markedly lower than the ones found in various aquatic species from different marine environments. The results presented in this study give relevant baseline data for environmental monitoring of organic pollution in coastal areas., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Metals are ubiquitous in the environment and accumulate in aquatic organisms and are known for their ability to enhance the production of reactive oxygen species (ROS). In aquatic species, oxidative stress mechanisms have been studied by measuring antioxidant enzyme activities and oxidative damages in tissues. The aim of this study was to apply and validate a set of oxidative stress biomarkers and correlate responses with metal contents in tissues of common octopus (Octopus vulgaris). Antioxidant enzyme activity (catalase--CAT, superoxide dismutase--SOD and glutathione S-transferases--GST), oxidative damages (lipid peroxidation--LPO and protein carbonyl content--PCO) and metal content (Cu, Zn, Pb, Cd and As) in the digestive gland and arm of octopus, collected in the NW Portuguese coast in different periods, were assessed after capture and after 14 days in captivity. CAT and SOD activities were highly responsive to fluctuations in metal concentrations and able to reduce oxidative damage, LPO and PCO in the digestive gland. CAT activity was also positively correlated with SOD and GST activities, which emphasizes that the three enzymes respond in a coordinated way to metal induced oxidative stress. Our results validate the use of oxidative stress biomarkers to assess metal pollution effects in this ecological and commercial relevant species. Moreover, octopus seems to have the ability to control oxidative damage by triggering an antioxidant enzyme coordinated response in the digestive gland., (Copyright © 2012 Elsevier B.V. All rights reserved.)

This study aimed to investigate the relationships between levels of organochlorine compounds (PCBs and DDTs), polycyclic aromatic hydrocarbons (PAHs), metals and biomarkers of exposure (EROD and GST) and oxidative stress biomarkers, in wild and cultured European seabass (Dicentrarchus labrax). Additionally, the fatty acid profile was determined in muscle to assess differences between cultivated and wild specimens of marketable size. Although results pointed to relatively low concentration of contaminants, wild specimens presented enhanced accumulation of metals and cultivated specimens higher levels of organic compounds. Biomarkers were correlated with contaminants in tissues, showing that higher levels can cause effects at the biochemical level. Wild specimens have presented higher content on omega-3 fatty acids in muscle. Besides the useful application of biomarkers in wild species, this study has shown that they can also be applied to monitor biological effects in the fish farming process., (Copyright 2010 Elsevier Inc. All rights reserved.)

Metals are environmentally ubiquitous and can be found at high concentrations in seawater and subsequently in marine organisms. Metals with high redox potential can trigger oxidative stress mechanisms with damaging effects in biological tissues. In aquatic species, oxidative stress has been evaluated by assessing antioxidant enzymes activities and oxidative damages in tissues. The purpose of this study was to evaluate oxidative stress biomarkers and metal residues in white seabream (Diplodus sargus), a species entering aquaculture production in Portugal. Metal residues (Cu, Cd, As and Pb), in liver and muscle, as well as oxidative stress biomarkers were assessed at different stages in the life cycle of white seabream under culture conditions and in wild specimens, of a marketable size. Metal concentrations in tissues were low, and below the established limits. However, wild white seabream showed higher accumulation than cultured ones. Antioxidant enzymes, namely catalase (CAT) and superoxide dismutase (SOD), were correlated with metal accumulation. Oxidative damages to tissues were low, with wild white seabream showing lower levels than cultured fish. This study showed that white seabream has a good antioxidant defense system, capable of reducing oxidative damages in tissues resulting from the presence of metals.

This study is part of a project aiming to validate the use of the intertidal shanny Lipophorys pholis as a sentinel species in pollution monitoring in NW European marine ecosystems. To this end, a characterisation of acethylcholin (AChE), butyrylcholin (BChE) and propionylcholin (PrChE) esterases in L. pholis muscle was performed and the results indicated that AChE was predominant. Furthermore, the use of eserine sulphate and BW284c51 (0.64-800 microM), and iso-OMPA (0.08-16 mM), confirmed the measurement of true cholinesterases (ChEs) as well as the presence of pseudocholinesterases. The field application of these markers to L. pholis, sampled in seven locations along the Portuguese coast, revealed that fish were likely to be affected by neurotoxic compounds. This was indicated by the significant depletion of AChE (p<0.05) in animals collected at urban and industrialised sites, compared with those from reference locations. The inclusion of a marker of effect, measured as lipid peroxidation levels in muscle tissue, also revealed the existence of site differences. Overall, the study further validates the utility of L. pholis in pollution monitoring studies.

Thirty three PCB congeners were analyzed in three size classes of seabass (Dicentrarchus labrax), from a semi-intensive fish farm, in food and in abiotic compartment. Water and suspended particulated matter (SPM) showed higher concentrations of lower chlorinated PCBs, whereas fish tissues and food showed higher concentrations of CB153 and CB138. In order to examine the influence of different inputs to seabass contamination, bioaccumulation factors (BAF), biota-suspended particulate matter bioaccumulation factors (BSMAF) and biomagnification factors (BMF) were calculated. In general, the log BAF and log BSMAF showed good correlations with log K(ow), for congeners with log K(ow)>6.1. In three fish size classes, PCB congeners with log K(ow)<6.1 were found at concentrations higher than what was expected based on the BAF calculated for the more hydrophobic congeners, suggesting a different contribution of sources. The application of a mass balance model for accumulation of some congeners in seabass estimated concentrations in fish 3- to 38-fold higher than the measured values, probably by overestimating gill absorption. The model was applied with other scenarios in order to maximize uptake from food, which may have a significant influence in accumulation, and not only from diet pellets. Its contribution to fish contamination for highly chlorinated PCBs may reach a maximum of 54-64%, and for lower chlorinated PCBs its contribution is lower than 20%. In this work it was proved that to reduce fish contamination the quality of the water should be controlled.

Specimens of Bolinus brandaris (neogastropod) were injected with a single dose of 500 ng/g body weight (b.w.) of tributyltin chloride (TBTCl) or triphenyltin chloride (TPTCl), or a mixture of both compounds (250 ng TBT/g b.w.+250 ng TPT/g b.w.), for a period of up to 31 days. At the end of 4 weeks, significant increases in the female penis size of those gastropods injected with TBT (P<0.05), TPT (P<0.05), or the mixture TBT+TPT (P<0.01) were recorded. In parallel, a group of animals was injected with the neuropeptide APGWamide but this compound failed to promote imposex, suggesting that APGWamide is not involved in imposex promotion in B. brandaris. Acetylcholinesterase activity, a biomarker of neurotoxicity, was determined in the neuroganglia at the end of the experiment, but no significant differences among treatments were found. Overall, these results support the hypothesis that TPT also acts as an endocrine disrupter in this neogastropod species. Our observations also highlight, for the first time, synergistic effects of organotin mixtures having imposex promotion as an endpoint.