Geochemical and Geophysical Monitoring of Hydrocarbon Seepage in the Adriatic Sea.

Hydrocarbon seepage is overlooked in the marine environment, mostly due to the lack of high-resolution exploration data. This contribution is about the set-up of a relocatable and cost-effective monitoring system, which was tested on two seepages in the Central Adriatic Sea. The two case studies are an oil spill at a water depth of 10 m and scattered biogenic methane seeps at a water depth of 84 m. Gas plumes in the water column were detected with a multibeam system, tightened to sub-seafloor seismic reflection data. Dissolved benthic fluxes of nutrients, metals and Dissolved Inorganic Carbon (DIC) were measured by in situ deployment of a benthic chamber, which was used also for the first time to collect water samples for hydrocarbons characterization. In addition, the concentration of polycyclic aromatic hydrocarbons, as well as major and trace elements were analyzed to provide an estimate of hydrocarbon contamination in the surrounding sediment and to make further inferences on the petroleum system.

Mercury Content in Central and Southern Adriatic Sea Sediments in Relation to Seafloor Geochemistry and Sedimentology.

Mercury contents were determined in surface sediments from the Central and Southern Adriatic Sea to gain insight into the processes, factors, and variables affecting its distribution. Mercury concentration was measured by thermal decomposition amalgamation atomic absorption spectrometry in samples collected by box-corer from Ancona to Santa Maria di Leuca during the CNR-PERTRE cruise (16/9-4/10/2016). Sediments were also evaluated for chemical-physical parameters (pH, Eh), biogeochemical composition (total carbon, inorganic carbon, total organic carbon, organic matter) and grain size. The average mercury concentration in the Adriatic Sea sediment was 0.053 mg/Kg (d.w.), range 0.011-0.12 mg/Kg (d.w.). Mercury content was mainly affected by grain size and organic matter (OM) distribution, whereas anthropic factors exerted a limited influence. Concentrations followed the distribution of sediment types (clay > silt > sand) due to Adriatic Sea hydrodynamics and were well below the regulatory limits in all samples.

Anthropogenic contribution, transport, and accumulation of Polycyclic Aromatic Hydrocarbons in sediments of the continental shelf and slope in the Mediterranean Sea.

A multidisciplinary approach, involving geochemical, sedimentological and oceanographic analyses, was employed to examine the distribution of Polycyclic Aromatic Hydrocarbons (PAHs) in a strongly anthropized area of the marginal Adriatic Sea (Mediterranean basin). The investigation into PAH distribution considered the grain size and biogeochemical properties of the sediments, as well as in relation to the main oceanographic processes and river inputs. Both biogeochemical and hydrographical inputs regulated the sedimentation of organic particles, influencing the distribution of PAHs. The results indicated PAH levels in 116 marine surface sediments ranging from 4 to 235 ng g-1 (average 55 ng g-1). The distribution of PAHs in Adriatic Sea surface sediments aligned with a higher clayey sedimentation in the deeper basin areas of the Middle Adriatic Depression.

Use of grape by-products in aquaculture: New frontiers for a circular economy application.

Grape by-products have already been used in cosmetics, food industries, but also animal feed industry, especially monogastrics and in aquaculture. Grape by-products have been studied for a long time and their principal activities are antimicrobial and antioxidant. Concerning aquaculture, the great demand and necessity to replace animal sources with vegetable ones, has placed grape by-products as possible new phytonutrients with beneficial properties. The purpose of this review is to describe the use of grape by-products in aquaculture, during the last decade, concerning their effects on: 1) gut health and welfare status; 2) growth performances; 3) quality of fillets and flesh during the rearing cycle and shelf-life products. Although other studies highlighted that the high supplementation of grape by-products could negatively affect fish health and growth, due to antinutritional factors (tannins), grape by-products are proven to be valuable phytonutrients that can be incorporated into fish feed to enhance growth and health during rearing conditions. Even in fish products, their utilization has proven to elongate the properties and shelf-life of fillets and minces. Further studies to evaluate the possible integrations or replacements with grape by-products in fish feed in order to evaluate their effectiveness in aquaculture from a sustainable circular economy perspective will be desirable to enhance the use of these products.

Impact of Modern Oven Treatments on Lipid Oxidation and Vitamin E Content of Fillets from Sardine (Sardina pilchardus) at Different Reproductive Cycle Phases.

The beneficial effects of sardine consumption can be related to the presence of bioactive compounds, such as vitamin E and ω3 polyunsaturated fatty acids. In any case, the levels of these compounds in sardine fillet depend on different factors mainly related to the diet and reproductive cycle phase of the fish as well as the technological treatments carried out to cook the fillets. The aim of the present study is two-fold: first, to evaluate changes in the total fatty acid profile, lipid oxidation, and vitamin E content of raw fillets from sardine (Sardina pilchardus) at different reproductive cycle phases (pre-spawning, spawning, and post-spawning); and second, to highlight how these nutritional profiles are affected by three oven treatments (conventional, steam, and sous-vide). For this purpose, raw fish was grouped into pre-spawning, spawning, and post-spawning phases according to the mesenteric fat frequency and the gonadosomatic index evaluation, and submitted to conventional (CO), steam (SO), and sous-vide (SV) baking. The ratio of EPA/DHA and vitamin E increased from post-spawning to pre-spawning, to spawning. Considering the reproductive phases, baking affected the oxidative degree differently: a CO > SO ≥ SV impact was found in the worst scenario (post-spawning), mitigated by vitamin E, to CO ≥ SO > SV in the best scenario (spawning). SV was the best treatment with high values of vitamin E in pre-spawning individuals (110.1 mg/kg). This study shows how vitamin E is correlated to the combined effect of endogenous and exogenous factors.

Mercury levels in Merluccius merluccius muscle tissue in the central Mediterranean Sea: Seasonal variation and human health risk.

In this study we analysed total mercury (THg) levels in European hake (Merluccius merluccius) - an ecologically and commercially important species throughout the Mediterranean - caught in the northern and central Adriatic Sea. To the best of our knowledge, this is the first study evaluating THg levels in hake fillets in relation to ecological (season) and biological (body size, sex, sexual maturity, lipid content) parameters. THg levels in muscle showed no sex-related differences; in contrast, significant season-related differences were found in females, with higher levels in spring-summer compared with autumn-winter. No season-related differences were seen in males. A significant sex effect was found for body size and sexual maturity. Females showed a correlation between THg level and length, THg being significantly higher in mature compared with immature specimens. No significant sex effect was found for muscle lipid content, because a correlation between THg concentration and tissue lipids was found in both sexes. Since the mean THg concentration found in M. merluccius fillets (0.64 ± 0.29 mg kg-1 dry weight; range, 0.20-1.53) was consistently under the level set by EU regulations, this study demonstrates that European hake caught in the northern and central Adriatic is safe for human consumption.

Occurrence and distribution of microbial pollutants in coastal areas of the Adriatic Sea influenced by river discharge.

The transport of a variety of pollutants from agricultural, industrial and urbanised areas makes rivers major contributors to the contamination of coastal marine environments. Too little is known of their role in carrying pathogens to the coast. We used DNA-based metabarcoding data to describe the microbial community composition in seawater and sediment collected in front of the estuary of the Tronto, the Chienti and the Esino, three Italian rivers with different pollution levels that empty into the north-central Adriatic Sea, and to detect and measure within these communities the relative abundance of microbial pollutants, including traditional faecal indicators and alternative faecal and sewage-associated pollutants. We then applied the FORENSIC algorithm to distinguish human from non-human sources of microbial pollution and FAPROTAX to map prokaryotic clades to established metabolic or other ecologically relevant functions. Finally, we searched the dataset for other common pathogenic taxa. Seawater and sediment contained numerous potentially pathogenic bacteria, mainly faecal and sewage-associated. The samples collected in front of the Tronto estuary showed the highest level of contamination, likely sewage-associated. The pathogenic signature showed a weak but positive correlation with some nutrients and strong correlations with some polycyclic aromatic hydrocarbons. This study confirms that rivers transport pathogenic bacteria to the coastal sea and highlights the value of expanding the use of HTS data, source tracking and functional identification tools to detect microbial pollutants and identify their sources with a view to gaining a better understanding of the pathways of sewage-associated discharges to the sea.

Assessment of seasonal relationship between polycyclic aromatic hydrocarbon accumulation and expression patterns of oxidative stress-related genes in muscle tissues of red mullet (M. barbatus) from the Northern Adriatic Sea.

In this study, we examined the seasonal association between Polycyclic Aromatic Hydrocarbon (PAH) concentrations and mRNA expression profiles of some antioxidant genes (i.e. CAT, GST and SOD), as well as lipid peroxidation (LPO), in muscle of sexually inactive females of red mullet (Mullus barbatus). Fish were captured in a fishery area of the Northern Adriatic Sea during both winter and summer. We found significantly (p < 0.05) higher ∑HMW-PAHs concentrations in muscle of specimens caught during winter than summer. On the basis of sampling season, red mullets exhibited different gene expression profiles of antioxidant enzymes showing lower levels of both CAT and GST in winter than in summer. Accordingly, CAT was found to be negatively associated with ∑PAH concentrations, especially ∑LMW-PAH, in individuals collected during winter. Seasonal-related downregulation of some oxidative stress biomarker expression is suggestive of greater susceptibility of red mullets to PAHs during winter.

Preliminary results on the occurrence and anatomical distribution of microplastics in wild populations of Nephrops norvegicus from the Adriatic Sea.

This study reports the shapes, dimensional classes, types and counts of microplastics (MPs) found in 23 individuals of N. norvegicus collected from two wild populations of the Adriatic Sea (Mediterranean basin). The focus was on three different anatomical compartments (gut, hepatopancreas and tail), which were analysed separately. MPs were found in all the investigated individuals with an average of about 17 MPs/individual. Fragments were predominant over fibers with a ratio of about 3:1. The majority of MPs were in the dimensional range 50-100 µm. The predominant polymers were polyester, polyamide 6, polyvinyl chloride and polyethylene, which together constitute about 61% of all the MPs found. Fragments were more concentrated in the hepatopancreas, with no significant difference between gut and tail, while fibers were more concentrated in the gut than in the tail with hepatopancreas somehow in between. The dimensional class of the MPs influences their anatomical distribution. There were no statistical differences among individuals from the two sampling sites. Sex of the individual did not influence the level of retained MPs, while length had a very marginal effect. The information reported here contributes to understanding of the possible risks linked to human consumption of different tissues from contaminated Norway lobsters.

Accumulation of PAHs in the tissues and algal symbionts of a common Mediterranean coral: Skeletal storage relates to population age structure.

Polycyclic aromatic hydrocarbons (PAHs) are widespread and harmful environmental pollutants that threaten marine ecosystems. Assessing their level and source is crucial to estimate the potential risks for marine organisms, as PAHs represent an additional threat to organism resilience under ongoing climatic change. Here we applied the QuEChERS extraction method to quantify four PAHs (i.e. acenaphthene, fluorene, fluoranthene, and pyrene) in three biological compartments (i.e. skeleton, tissue, and zooxanthellae symbiotic algae) of adult and old specimens of a scleractinian coral species (Balanophyllia europaea) that is widespread throughout the Mediterranean Sea. A higher concentration of all four investigated PAHs was observed in the zooxanthellae, followed by the coral tissue, with lowest concentration in the skeleton, consistently with previous studies on tropical species. In all the three biological compartments, the concentration of low molecular weight PAHs was higher with respect to high-molecular weight PAHs, in agreement with their bioaccumulation capabilities. PAH concentration was unrelated to skeletal age. Observed PAHs were of petrogenic origin, reflecting the pollution sources of the sampling area. By coupling PAH data with population age structure data measured in the field, the amount of PAHs stored in the long term (i.e. up to 20 years) in coral skeletons was quantified and resulted in 53.6 ng m-2 of acenaphthene, 69.4 ng m-2 of fluorene, 2.7 ng m-2 of fluoranthene, and 11.7 ng m-2 of pyrene. This estimate provides the basis for further assessments of long-term sequestration of PAHs from the marine environment in the whole Mediterranean, given the widespread distribution of the investigated coral species.

Meiofaunal communities in four Adriatic ports: Baseline data for risk assessment in ballast water management.

Ports receive a variety of contaminants related to a wide range of anthropogenic activities - including ship ballast water (BW) - that ultimately find their way to sediments. Benthic meiofauna from four Adriatic ports (Ancona, Trieste, Koper, and Split) was assessed for the main environmental pollutants, to evaluate the effects of human activities on meiobenthos and identify the most appropriate descriptor to assess the ecological quality of marine ecosystems. Sediment analysis demonstrated that Trieste and Split were the most contaminated ports, followed by Koper and Ancona. All meiofaunal parameters showed high spatial and temporal variability, in line with the marked heterogeneity of the four ports. Sand, total organic carbon, and pollutants seemed to be the variables that best explained meiofaunal patterns. Community structure and rare taxa were the meiofaunal descriptors that reflected the environmental status and biological response most accurately. The present data suggest that meiofauna can be used to assess the biological impact of BW.

Polycyclic aromatic hydrocarbon (PAH) accumulation in different common sole (Solea solea) tissues from the North Adriatic Sea peculiar impacted area.

This study extends our knowledge of the bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) in marine organisms and investigates its possible determinants. PAH levels were measured in Solea solea tissue and in marine sediments collected from three areas of the northern Adriatic Sea characterized by different anthropic impacts (Venetian Lagoon, Po Delta, and fishing grounds off Chioggia). The possibility of differential PAH bioaccumulation in different tissues (muscle, liver and gills) was investigated by seeking relationships between mean individual and total PAH concentrations in tissue and sediment samples, the physicochemical properties of PAHs (rings and Kow), and some key biological variables (lipid content of tissues, body size, habitat). The present study demonstrated that the lipid content might not be the only determinant of PAH bioaccumulation in common sole tissues. The habitat characteristics, the tissue types and some physicochemical properties of compounds were closely related to PAH bioaccumulation.

Investigating the potential impact of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) on gene biomarker expression and global DNA methylation in loggerhead sea turtles (Caretta caretta) from the Adriatic Sea.

Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) are priority contaminants that bioaccumulate through the food webs and affect the biology of a variety of resident and migratory species, including sea turtles. Few studies have evaluated toxicological biomarkers of exposure to PAHs and PCBs in these animals. The present paper reports the results of an initial field study to quantify the association between plasma concentrations of PAHs/PCBs and whole blood cell expression of gene biomarkers in juvenile loggerhead sea turtles (Caretta caretta) rescued along the Italian coasts of the northern and central areas of the Adriatic Sea. While detectable levels of PAHs were found in all plasma samples examined, only three PCB congeners (PCB52, PCB95, and PCB149) were noted, with detection percentages ranging between 48% and 57%. A significant correlation was found between 3 of the 6 gene biomarkers assessed (HSP60, CYP1A and ERα) and plasma levels of some PAH congeners. In contrast, no significant association between PCB burden and gene expression was observed. The global DNA methylation levels were significantly and positively correlated with the concentrations of most of the PAHs and only one of the PCB congeners (PCB52). The relation between PAH concentration and gene expression in whole blood cells suggests that these genes may respond to environmental contaminant exposure and are promising candidates for the development of biomarkers for monitoring sea turtle exposure to persistent organic pollutants (POPs).

Alterations of gene expression indicating effects on estrogen signaling and lipid homeostasis in seabream hepatocytes exposed to extracts of seawater sampled from a coastal area of the central Adriatic Sea (Italy).

Recent evidences suggest that the toxicological effects of endocrine disrupting chemicals (EDCs) involve multiple nuclear receptor-mediated pathways, including estrogen receptor (ER) and peroxisome proliferator-activated receptor (PPAR) signaling systems. Thus, our objective in this study was to detect the summated endocrine effects of EDCs with metabolic activity in coastal waters of the central Adriatic Sea by means of a toxicogenomic approach using seabream hepatocytes. Gene expression patterns were also correlated with seawater levels of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs). We found that seawater extracts taken at certain areas induced gene expression profiles of ERα/vitellogenin, PPARα/Stearoyl-CoA desaturase 1A, cytochrome P4501A (CYP1A) and metallothionein. These increased levels of biomarkers responses correlated with spatial distribution of PAHs/PCBs concentrations observed by chemical analysis in the different study areas. Collectively, our data give a snapshot of the presence of complex EDC mixtures that are able to perturb metabolic signaling in coastal marine waters.

Do lagoon area sediments act as traps for polycyclic aromatic hydrocarbons?

The coastal lagoons are vulnerable systems, located between the land and the sea, enriched by both marine and continental inputs and are among the most productive aquatic ecosystems. The purpose of this work is to understand the influence of the lagoon area sediments on the behaviour of polycyclic aromatic hydrocarbons, through the adsorption coefficient determination. In fact, the sorption of polycyclic aromatic hydrocarbons is an important process because it governs the fate, transport, bioavailability and toxicity of these compounds in sediments. It has been observed that the adsorption of polycyclic aromatic hydrocarbons in a transitional system is the outcome of different factors, such as their sources and physicochemical properties, salinity and sediment composition, hydrology and environmental conditions. The results showed that transitional areas contribute to the polycyclic aromatic hydrocarbon accumulation in the sediment turning it into a trap.

Persistence of polycyclic aromatic hydrocarbons in sediments in the deeper area of the Northern Adriatic Sea (Mediterranean Sea).

The Po Valley is the most important agricultural and industrial area of Adriatic basin. In this area there are several rivers which transport polycyclic aromatic hydrocarbons (PAHs) into the sea via suspended particulate matter. This study describes the persistence of PAHs in the deep and coastal sediments of the Northern Adriatic. Different environmental conditions were studied: salinity, temperature, sunlight, sediment particle size and organic matter in sediment. The average conditions in the deep areas of the Northern Adriatic are: salinity higher than 37, temperature lower than 11 °C, darkness and clayey sediments with a high organic matter content. These conditions increase the persistence of the PAHs in the deep area of the Northern Adriatic.