Mugilidae fish as bioindicator for monitoring plastic pollution: Comparison between a commercial port and a fishpond (north-western Mediterranean Sea).

In the last decade, interest in monitoring and managing plastic pollution has greatly increased. This study compared levels of microplastic contamination in stomachs of Mugilidae fish, suggesting this family as a target for plastic pollution monitoring in areas with different degrees of anthropisation. Two sites characterised by low and high anthropic impact, a fishpond (S'Ena Arrubia, Italy) and a port (Genoa, Italy), respectively, were compared. This study highlighted a stronger microplastic contamination in the port, with a higher percentage of fish showing the presence of microplastics and a larger polymeric variability compared to the fishpond. The microplastic number in fish from the port was higher than in the literature, but it was not significantly different from S'Ena Arrubia in terms of the microplastic percentage found in single individuals. Biomonitoring of microplastic contamination in Mugilidae fish resulted in a valid tool for the investigation of areas differently affected by human activity.

Microplastics in the abyss: a first investigation into sediments at 2443-m depth (Toulon, France).

Plastic and microplastic pollutions are known to be widespread across the planet in all types of environments. However, relatively little about microplastic quantities in the deeper areas of the oceans is known, due to the difficulty to reach these environments. In this work, we present an investigation of microplastic (<5 mm) distribution performed in the bottom sediments of the abyssal plain off the coast and the canyon of Toulon (France). Four samples of deep-sea sediment were collected at the depth of 2443 m during the sea operations carried out by the French oceanographic cruises for the KM3NeT project. The chemical and physical characterisation of the sediment was carried out, and items were extracted from sediments by density separation and analysed by optical microscope and µRaman spectroscopy. Results show microplastics in the deep-sea sediments with a concentration of about 80 particles L-1, confirming the hypothesis of microplastics spread to abyssal sediments in the Mediterranean Sea.

Baseline on rare earth elements in the marine sediments of a Mediterranean commercial port as environmental tracers and their relationships with inorganic contaminants.

The Port of Genoa (north-western Mediterranean Sea) receives sediments from two different catchment areas (Bisagno and Polcevera torrents). The aim of the work is to evaluate if Rare Earth Elements (REEs) could be used to identify the two sedimentary inputs and to unravel the origin of inorganic contaminants in an anthropised basin. REE results constitute a baseline for this port. The main REE-bearing minerals are phosphates and zircon. As, Cd, Hg, Pb, and Sn concentrate in the sediments closer to the Bisagno Torrent mouth, and the correlation with Ca and Light-REEs suggests their plausible geological origin. Co, Mn, and Ni maxima lie in the sediments closer to the Polcevera Torrent. Their correlation with Middle-REEs and Mg suggest that ophiolitic rocks could explain their presence. Cr, Cu, V, and Zn do not show a clear correlation with REEs, and their origin probably is a combination of natural and anthropogenic sources.

Sediment distribution on the continental shelf in relation to stream inputs and contamination: hydrodynamic, chemical, mineralogical, and sedimentological characteristics (Ligurian Sea, Italy).

River estuaries, continental shelf, and sediment contamination are closely linked from the point of view of sediment transport and diffusion that is governed by different factors such as sea waves and currents, river flows and floods, and sediment characteristics. Taking these factors into consideration, we have examined marine environmental and marine bottom sediments off the mouth of a stream to highlight the main ways of sediment and contaminant transport and diffusion on the continental shelf. For this purpose, we followed a multidisciplinary approach, studying circulation of water masses, hydrological characteristics of water column, distribution and main characteristics of sediment grain size, sediment mineralogical composition, and metal concentrations of bottom sediments. Our results allowed identifying the presence of preferential ways of sediment deposition and areas of sediment spread for the Entella Stream, as well as the origin of some metals.

Baseline of distribution and origin of Rare Earth Elements in marine sediment of the coastal area of the Eastern Gulf of Tigullio (Ligurian Sea, North-West Italy).

A study on the Rare Earth Element (REE) distribution in the bottom sediments of the Gulf of Tigullio (north-west Italy) was conducted. The results constitute a baseline for this zone of the Ligurian Sea and enabled the obtaining of valuable information on the origin and transport of sediments in the gulf. The distribution of REEs is controlled by phosphates, mainly monazite, and is generally homogeneous in the study area, reflecting the homogeneous distribution of the minerals. Some differences in REE and Sc distribution allow us to identify two sub-basins (Entella and Gromolo torrent sub-basins) characterised by slightly different geological frameworks. The "hat-shaped" observed patterns seem to indicate an overprinting of the original REE patterns due to exchanges between phosphates and seawater. REEs seem to be related with the rocks outcropping in the area, although an indirect effect of anthropic activity could be seen near a fish farm.

Environmental implications of metal mobility in marine sediments receiving input from a torrent affected by mine discharge.

Acid Mine Drainage (AMD) is one of the most important sources of pollution in fluvial systems and can enrich rivers in dissolved and suspended metals of environmental concern. Colloidal particles may favour the transport of metals to the sea, where metals can be accumulated in bottom sediments. The aim of this paper was to evaluate the mobility of metals in the "Baia delle Favole" bottom sediments (Sestri Levante, Italy), which receive the input of the AMD impacted Gromolo Torrent, using chemical speciation (BCR sequential extraction). Basing on the Risk Assessment Code (RAC), our results showed a systematic and widespread high risk classification for Mn, whereas a medium risk is associated to Co, Cu, and Zn in the sediments collected near the mouth of the Gromolo Torrent. Moreover, in these sediments the occurrence of Fe oxyhydroxides has been observed, reflecting an increase of metals in the reducible fraction obtained with BCR.

Benthic diatom community response to metal contamination from an abandoned Cu mine: Case study of the Gromolo Torrent (Italy).

Environmental contamination has become a global problem of increasing intensity due to the exponential growth of industrialization. One main debated issue is the metal contamination of rivers receiving Acid Mine Drainage (AMD) from active/abandoned mines. In order to assess the quality of lotic systems, diatoms are commonly used, as their assemblage modifies on the basis of changes in environmental parameters. Benthic diatom changes were analyzed along the metal-impacted Gromolo Torrent (Liguria, NW Italy) with the aim of understanding the effects of input from the abandoned Libiola Cu mine. The results support the hypothesis that metals from AMD lead to massive changes in diatoms, resulting in low biological diversity and in a shift of dominance, passing from the genera Cymbella and Cocconeis to more tolerant and opportunistic species, such as Achnanthidium minutissimum and Fragilaria rumpens. The high concentrations of labile metals, measured through Diffusion Gradients in Thin-films (DGT) immediately downstream of the two AMD inputs in the torrent, corresponded to a sudden decrease in the presence of diatoms, indicating the possible reaching of acute toxic levels. In particular, A. minutissimum dominated the mining area and was positively correlated with Cu and Zn; whereas F. rumpens bloomed downstream of this area, where the metal content was diluted, and was positively correlated with As and Pb. Finally, an important abundance of Nitzschia palea and teratological forms of A. minutissimum and F. rumpens were observed downstream from the mine, indicating that metals may have an important impact on diatoms up to the torrent mouth.

A Novel Synthesis Routine for Woodwardite and Its Affinity towards Light (La, Ce, Nd) and Heavy (Gd and Y) Rare Earth Elements.

A synthetic Cu-Al-SO4 layered double hydroxide (LDH), analogue to the mineral woodwardite [Cu1-xAlx(SO4)x/2(OH)2·nH2O], with x < 0.5 and n ≤ 3x/2, was synthesised by adding a solution of Cu and Al sulphates to a solution with NaOH. The pH values were kept constant at 8.0 and 10.0 by a continuous addition of NaOH. The material obtained had poor crystallinity, turbostratic structure, and consisted of nanoscopic crystallites. The analyses performed in order to characterise the obtained materials (X-ray diffraction (XRD), thermogravimetry (TG), and Fourier Transform Infra-Red (FTIR) spectroscopy) showed that the Cu-Al-SO4 LDH is very similar to woodwardite, although it has a smaller layer spacing, presumably due to a lesser water content than in natural samples. The synthesis was performed by adding light rare earth elements (LREEs) (La, Ce, and Nd) and heavy rare earth elements (HREEs) (Gd and Y) in order to test the affinity of the Cu-Al-SO4 LDH to the incorporation of REEs. The concentration of rare earth elements (REEs) in the solid fraction was in the range of 3.5-8 wt %. The results showed a good affinity for HREE and Nd, especially for materials synthesised at pH 10.0, whereas the affinities for Ce and La were much lower or non-existent. The thermal decomposition of the REE-doped materials generates a mixture of Cu, Al, and REE oxides, making them interesting as precursors in REE oxide synthesis.

Metal transport and remobilisation in a basin affected by acid mine drainage: the role of ochreous amorphous precipitates.

Metal-polluted mine waters represent a major threat to the quality of waters and sediments in a downstream basin. At the confluence between acidic mine waters and the unpolluted waters of the Gromolo Torrent (Liguria, North-West Italy), the massive formation of an ochreous amorphous precipitate takes place. This precipitate forms a soft blanket that covers the torrent bed and can be observed down to its mouth in the sea. The aim of this work is to evaluate the dispersion of metals in the Gromolo Torrent basin from the abandoned Cu-Fe sulphide mine of Libiola to the Ligurian Sea and to assess the metal remobilisation from the amorphous precipitates. The mineralogy of the superficial sediments collected in the torrent bed and the concentrations of different elements of environmental concern (Cu, Zn, Cd, Co, Cr, Mn, Ni, Pb, As, and Sb) were therefore analysed. The results showed that the precipitates contain high concentration of Fe, Al, Cu, and Zn, significantly modifying the bulk chemistry of the Gromolo Torrent sediments. In order to evaluate the possible remobilisation of ecotoxic elements from the amorphous precipitates, bulk leaching tests were performed with both deionised and seawater. Bulk leaching tests with deionised water mobilised primarily high Pb amounts, but also relatively high concentrations of Fe, Al, Cu, and Zn are released in the leachate. In seawater tests, Fe, Al, Cu, and Zn were released in smaller amounts, while other elements like Mn, Cd, Co, and Ni increased in the released fraction. Pb was still strongly released as in deionised water experiments. The results show that the interaction of precipitates and seawater can remobilise high concentrations of metals, thus affecting the surrounding environment.