PAHs and trace metals in marine surficial sediments from the Porcupine Bank (NE Atlantic): A contribution to establishing background concentrations.

Little is known about pollutant concentrations in marine remote areas such as the Porcupine Bank in the NE Atlantic Ocean. Remote locations are much less studied than the more readily accessible coastal areas, nevertheless, are of great importance both to unveil how far human influence has reached and, are more challenging, to infer background concentrations (BCs) of naturally occurring and/or anthropogenic pollutants. Knowledge of contaminant background levels are critical for establishing remediation and management strategies; in addition, background assessment is heavily emphasised in legislative monitoring requirements. Obtaining suitable sampling locations to assess background concentrations can be challenging, as samples should match characteristics to the target area and not be impacted by historical or current inputs of the chemical substances of study. Anthropogenic impacts generally deem local-based sampling to be unsuitable to infer background pollution values. Sampling in remote areas such as the Porcupine Bank better fulfils low impact and pressure requirements making them more suitable for the derivation of background concentration estimates for organic compounds and metals. The total concentrations of polycyclic aromatic hydrocarbons (PAHs) and metal(loid)s in deep sea sediments were evaluated and both an environmental status and a set of concentration data were adequate to derive BCs concentrations is presented. Concentration data indicated, in comparison with previous published data, trace level presence of PAHs and metal(loids) in sediments from the Porcupine Bank. These values will provide a valuable tool to identify the natural presence of organic and inorganic compounds and be the basis to perform a sound environmental assessment.

Use of limpets as alternative to mussels in metal pollution monitoring; application in the Canary Islands.

Metal pollution monitoring programs make use of organisms, such as mussels, as biomonitors to evaluate and compare the metal pollution status of coastal areas worldwide. Despite the widespread distribution of mussels of the genus Mytilus, there are places where these organisms are absent or where their abundance is insufficient for biomonitoring purposes, such as in the Canary Islands (Spain). This study considers the use of limpets of the genus Patella as alternative/complementary species in metal pollution monitoring, and compares the bioaccumulation capacity of mussels and limpets collected simultaneously during several sampling campaigns at 11 sampling sites along the continental Spanish Atlantic coastline. Results show that there are some differences in bioaccumulation capacity between limpets and mussels, with limpets showing in average higher concentrations of Cd, Cr, Ni, As and Cu, and lower concentrations of Zn, while concentrations of Hg and Pb were similar for both types of organisms. Significant correlations between metal concentration in mussels and limpets were found for most metals, with the notable exception of Cd, that showed a very different bioaccumulation pattern in both types of organisms. Limpet to mussel metal concentration ratios were derived that can be used to compare the results of metal biomonitoring using either limpets or mussels, and limpets were successfully used in a monitoring survey in the Canary Islands.

Impact assessment of a large river on the sediments and fish from its continental shelf: using Solea solea as sentinel in the Ebro river mouth (NW Mediterranean, Spain).

Many studies have been carried out along mighty rivers with heavily industrialized watersheds to evaluate pollutants and their effects on freshwater organisms. However, their impact on marine organisms is virtually unknown. In order to cover this gap, Solea solea, one of the most important commercial fish species, together with sediments, were sampled during 2013-2015 offshore from the Ebro Delta river mouth. Fish health indicators (condition indices, histological tissue alterations, and parasite descriptors) were used to assess the potential effect of pollutants, an issue of particular interest in the area following the dredging activities taking place in the river upstream in 2013. No major histopathological alterations were detected, but perivascular inflammatory foci (PIF) were frequently observed, especially in 2014. The most prevalent and abundant parasites were acanthocephalans and digeneans within the digestive tract and copepods on the gills. Levels of trace metals from sediments and fish muscle were below the effects range median and reference levels accepted for human consumption, respectively. However, the lower levels of the hepatosomatic index, higher numbers of PIF, and variations in the abundance of parasites in 2014 and 2015 could suggest a pollutant exposure during these years. These results warn signs of toxicity, which could be associated with sediment leaks during the dredging activities.

Trace Metal Residues in Marine Mussels: A Global Survey.

Pressures from anthropogenic activities are causing degradation of estuarine and coastal ecosystems around the world. Trace metals are key pollutants that are released and can partition in a range of environmental compartments, to be ultimately accumulated in exposed biota. The level of pressure varies with locations and the range and intensity of anthropogenic activities. The present study measured residues of trace metals in Mytilus mussel species collected from a range of locations around the world in areas experiencing a gradient of anthropogenic pressures that we classified as low, moderate, or high impact. The data showed no grouping/impact level when sampling sites in all countries were incorporated in the analysis, but there was significant clustering/impact level for most countries. Overall, high-impact areas were characterized by elevated concentrations of zinc, lead, nickel, and arsenic, whereas copper and silver were detected at higher concentrations in medium-impact areas. Finally, whereas most metals were found at lower concentrations in areas classified as low impact, cadmium was typically elevated in these areas. The present study provides a unique snapshot of worldwide levels of coastal metal contamination through the use of Mytilus species, a well-established marine biomonitoring tool. Environ Toxicol Chem 2021;40:3434-3440. © 2021 SETAC.

Sea snail (Hexaplex trunculus) and sea cucumber (Holothuria polii) as potential sentinel species for organic pollutants and trace metals in coastal ecosystems.

The seasonal bioaccumulation of trace metals, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorinated pesticides (OCPs) in sea snail (Hexaplex trunculus) and sea cucumber (Holothuria polii) from Mar Menor lagoon were characterised. The highest concentrations of p,p'-DDE were detected in the central and south part of Mar Menor lagoon. However, the highest concentrations of metals in sea snail and holothurians were detected in the influence area of El Beal wadi. Biomagnification factors (BMF) in sea snail from cockle (sea snail-cockle concentration ratio) were higher than 5 for metal and organochlorinated compounds. However, similar concentrations were observed in both species for PAHs due to gastropods capability of metabolising these pollutants. Consequently, sea snail is proposed as a sentinel for trace metals, PCBs and OCPs in the coastal lagoons, not only due to its bioaccumulation and biomagnification capacity but also the easy sampling and amply distribution in many coastal areas.

Yellow-legged gull eggs (Larus michahellis) as persistent organic pollutants and trace metal bioindicator for two nearby areas with different human impact.

The concentration of different persistent organic pollutants (POPs including chlorinated and brominated compounds) and trace metals and metalloids (As, Cd, Cu, Cr, Pb, Hg, Ni, and Zn) was examined in eggs from two colonies of yellow-legged gulls. The two colonies are established in Ría de Vigo, Northwest Spain, with a distance between them of only 10 km, one in Vigo town (industrial and harbour activities) and the other in the Cíes Islands in a Natural Park and Marine Protected Area -MPA- (with no known anthropogenic inputs). Statistically significant differences for the two colonies were observed for Hg, the sum of 7 CBs, the sum of DDTs y and the sum of 9 PBDEs, with values that could be causing some toxic effects in the area of the most anthropogenically influenced colony. The estimated isotopic niche was also calculated, based on δ15N and δ13C, for the two colonies, pointing to a wider diet in the Cíes colony when compared to the diet in the Vigo colony. The study supports the use of the yellow-legged seagull eggs as a bioindicator of pollution capable of differentiating pollution level even in geographically close areas.

A new perspective on marine assessment of metals and organic pollutants: A case study from Bay of Santander.

Pollution assessment is worldwide generally performed based on 'Trend assessment' or 'Status assessment´, and usually requires monitoring programs that should be designed in terms of pollutants to be studied, frequency and locations. Five groups of pollutants: polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs) and trace metals, were selected to evaluate how actual monitoring programs are coping with the evaluation of anthropogenic activities affect the environment and whether use restrictions and laws that ban certain pollutants are being effective. Santander Bay, in Northern Spain, is an industrial area with 250,000 inhabitants and with several rivers discharging into the Bay; those characteristics made the area an adequate location to perform the study. Marine sediment was selected as the study matrix since it gives comprehensive information regarding the human activities in coastal areas. The study clearly shows that there can be some potential biological impacts on the marine environment due to PAHs (mainly BghiP), PCBs (mainly congener CB118) and metals. On the other hand all analysed OCPs and PBDEs presented values below the applicable guidelines and will therefore, in principle, not give rise to environmental problems. Consequently, even after decades of banning and use restrictions, the studied pollutants are still a main issue in coastal areas. Moreover, the present study helps in the definition of future monitoring programs providing a complete description about the current situation of the listed pollutants.

Ingestion of microplastics by demersal fish from the Spanish Atlantic and Mediterranean coasts.

Microplastic pollution has received increased attention over the last few years. This study documents microplastic ingestion in three commercially relevant demersal fish species from the Spanish Atlantic and Mediterranean coasts, the lesser spotted dogfish Scyliorhinus canicula, the European hake Merluccius merluccius and the red mullet Mullus barbatus. Overall 212 fish were examined, 72 dogfish, 12 hakes and 128 red mullets. The percentage of fish with microplastics was 17.5% (15.3% dogfish, 18.8% red mullets and 16.7% hakes), averaging 1.56±0.5 items per fish, and the size of the microplastics ranged from 0.38 to 3.1mm. These fish species are used currently as biomonitors for marine pollution monitoring within the Spanish Marine Pollution Monitoring Programme (SMP), and may be as well suitable candidates for monitoring spatial and temporal trends of ingested litter. The data presented here represent a baseline for the implementation of the Marine Strategy Framework Directive descriptor 10 in Spain.

Evidence of increased anthropogenic emissions of platinum: time-series analysis of mussels (1991-2011) of an urban beach.

The anthropogenic emissions of Pt to the environment have increased significantly over the past decades, especially after the introduction of the catalytic converters in motor vehicles. In order to check whether this is affecting the levels of this trace metal on living organisms, time-series analysis of freeze-dried soft tissue material of wild mussels (Mytilus galloprovincialis) covering the period from 1991 to 2001 and collected at an urban beach in the city of Vigo (NW Iberian Peninsula) was conducted. Concentrations ranged from 0.30 to 0.68 ng g(-1) with an average concentration of 0.47 ± 0.10 ng g(-1) (n=21); these concentrations were higher than those obtained for samples collected at a control location away from anthropogenic pressure (0.31 ± 0.10 ng g(-1); n=5). Platinum concentrations followed a statistically significant temporal trend (at the 0.020 level), and the excess of Pt in mussels over the 1991-2011 period compared to the control location were correlated with the European Pt autocatalyst demand (p=0.0006) and, especially, the car sales in Spain (p=0.0001). A bioaccumulation factor of ~5·10(3) was derived, which is greater than those previously calculated for Pt from exposure experiments, but 1-2 orders of magnitude lower than other trace elements (e.g. Zn, Cu, Pb, Cd).

Influence of mussel biological variability on pollution biomarkers.

This study deals with the identification and characterization of biological variables that may affect some of the biological responses used as pollution biomarkers. With this aim, during the 2012 mussel survey of the Spanish Marine Pollution monitoring program (SMP), at the North-Atlantic coast, several quantitative and qualitative biological variables were measured (corporal and shell indices, gonadal development and reserves composition). Studied biomarkers were antioxidant enzymatic activities (CAT, GST, GR), lipid peroxidation (LPO) and the physiological rates integrated in the SFG biomarker (CR, AE, RR). Site pollution was considered as the chemical concentration in the whole tissues of mussels. A great geographical variability was observed for the biological variables, which was mainly linked to the differences in food availability along the studied region. An inverse relationship between antioxidant enzymes and the nutritional status of the organism was evidenced, whereas LPO was positively related to nutritional status and, therefore, with higher metabolic costs, with their associated ROS generation. Mussel condition was also inversely related to CR, and therefore to SFG, suggesting that mussels keep an "ecological memory" from the habitat where they have been collected. No overall relationship was observed between pollution and biomarkers, but a significant overall effect of biological variables on both biochemical and physiological biomarkers was evidenced. It was concluded that when a wide range of certain environmental factors, as food availability, coexist in the same monitoring program, it determines a great variability in mussel populations which mask the effect of contaminants on biomarkers.

An assessment of two decades of trace metals monitoring in wild mussels from the Northwest Atlantic and Cantabrian coastal areas of Spain, 1991-2011.

Since 1991, the Instituto Español de Oceanografía has monitored the concentrations of trace metals in wild mussels from the north (Cantabrian Sea) and northwest (Atlantic) coasts of Spain to define geographical distributions and temporal trends. While Cu, Zn and As concentrations presented fairly uniform geographical distributions, Hg and Pb concentrations were higher in mussels from the Cantabrian sea region as a result of historical anthropogenic activities. Cd, on the other hand, appeared to be more affected by natural processes on the northwest Atlantic coast (i.e., upwelling) than by human activity. Approximately 70% of the paired observations showed downward trends, 50% of these significant, with time. An improvement in environmental conditions along the northern coasts of Spain is evident despite that some metal levels resulted above the Background Assessment Concentrations given by OSPAR to assess potentially harmful occurrences.

Combined use of chemical, biochemical and physiological variables in mussels for the assessment of marine pollution along the N-NW Spanish coast.

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.

First measurements of the scope for growth (SFG) in mussels from a large scale survey in the North-Atlantic Spanish coast.

SFG and physiological rates were measured in wild mussels from the Spanish Marine Pollution monitoring program (SMP) in order to determine seawater quality. It consists of 41 stations, covering almost 2500 km of coast, making the SMP the widest-ranging monitoring network in the Iberian Peninsula's Atlantic region. Results of the 2007 and 2008 surveys when 39 sites were sampled: (20 in 2007 and 19 in 2008, being 8 sites sampled both years) were presented. Chemical analyses were carried out to determine the relationships between physiological rates and the accumulation of toxic compounds. Data presented are the first to become available on the use of SFG as a biomarker of the marine environment on a large spatial scale (>1000 km) along Spain's Atlantic seaboard. SFG values enable significant differences to be established between the areas sampled and between the two years surveyed. The integration of biological and chemical data suggests that certain organochlorine compounds, namely chlordanes and DDTs, may have a negative effect on SFG, although such an effect is of a lesser magnitude than that associated with certain biological parameters such as condition index and mussel age. These variables act as confounding factors when attempting to determine the effect of chemical compounds present in the marine environment on mussel SFG. Further research is therefore needed on the relation between these confounding factors and SFG in order to apply the relevant corrective strategies to enable this index to be used in monitoring programs. The effect of these confounding factors is more clearly revealed in studies that cover a wide-ranging spatial and time scale, such as those carried out within the SMP. These results do not invalidate the use of biological data in monitoring programs, but rather point to the need to analyze all the factors affecting each biological process.

Linking chemical contamination to biological effects in coastal pollution monitoring.

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.

Chemometric tools to evaluate the spatial distribution of trace metals in surface sediments of two Spanish rías.

A suite of relevant trace metals (Hg, Pb, Cd, Cu, Zn and Ni) was measured in surface sediment samples to assess the environmental situation of the largest two Atlantic Spanish 'rías' (a form of estuaries, ría of Pontevedra, ROP, and ría of Vigo, ROV). The level of contamination originated by these metals was assessed against international guidelines, the threshold effect, ERL, and the midrange effect, ERM. Six unsupervised and supervised multivariate chemometric techniques were applied to model each ría, compare them and select those metals that characterize the samples. This is first time that such a study is performed for these two important seafood-producing areas. Maximum concentrations at ROP occurred in the vicinities of an inner island, where Cu, Zn, Ni and Pb presented concentrations over the ERL and Hg over the ERM. Highest concentrations of metals in ROV were observed in the proximities of Vigo shipyards and port, except for Pb, with peak values in San Simon Bay. ERL limits were exceeded in the inner part of this ría for Cu, Zn and Hg and in a wider area for Pb and Ni. Levels for Pb went beyond the ERM boundary in the axial part of San Simon Bay. In general, the distribution of the metals was more homogeneous in ría of Pontevedra than in ría of Vigo (where three morphological zones were characterized). Both rías could be differentiated using only two metals: Ni and Hg, as deduced from the multivariate techniques.

Comparison of the 2000 and 2005 spatial distributions of heavy metals in wild mussels from the North-Atlantic Spanish coast.

Spatial distributions of Cd, Cu, Hg, Pb and Zn in Mytilus galloprovincialis in 41 sampling sites in the North-Atlantic Spanish coast were monitored in 2000 and 2005 to assess the coastal environmental pollution. A pool of mussel soft tissue was prepared using 50 or more individuals representing the available size range. Samples were grounded, homogenised and quantified by atomic absorption spectrometry. Quality of the chemical analyses was assessed by participation in periodic interlaboratory exercises. Univariate and multivariate statistical studies, Principal Components Analysis and Procrustes rotation (a technique intended to compare several data spaces) were carried out. Some decreasing trends were observed for the concentrations throughout the 2000-2005 period, mainly for Hg and Pb. In general, the Northern area showed higher median concentrations (e.g., 3.79 and 4.28 mg Pb/kg dry weight, and 0.160 and 0.191 mg Hg/kg dry weight, for 2000 and 2005, respectively) than the Atlantic ones (e.g., 1.47 and 1.44 mg Pb/kg dry weight, and 0.097 and 0.084 mgHg/kg dry weight, for 2000 and 2005, respectively). Nevertheless, some Atlantic sampling points, located far from human inputs (cities, industries, rivers, etc.) exhibited high concentrations of Cd, which was attributed to the influence of the natural upwelling processes which occur annually in that geographical region.