Electrochemical remediation of synthetic and real marine sediments contaminated by PAHs, Hg and As under low electric field values.

To date, remediation, protection, and restoration of contaminated sites is a global concern. The current technologies to restore sediments characterized by heterogeneous characteristics, several pollutants, fine grains, and low hydraulic permeability are poorly effective; hence their remediation is still challenging. A promising approach for the sediment's remediation could be the electrochemical route since it is a not-expensive, effective and noninvasive in situ technology. Electrochemical remediation (ER) is commonly studied under relatively high electric fields (E ≥ 1 V cm-1) and using costly processing fluids in a three compartments cell aiming to desorb and transport the contaminants into the processing fluids (secondary dangerous effluent). In this work, contaminated marine sediments were electrochemically treated focusing on the insertion of electrodes directly in the sediments and adopting, for the first time for real sediments, low E values (≤ 0.25 V cm-1) for 4-days period. It was observed that PAHs can be simultaneously transported and degraded in situ preventing the production of a secondary dangerous effluent and reducing the energy consumption. Firstly, clay marine sediments dragged from Capo Granitola Coast (Trapani, Italy) spiked with five PAHs congeners (5PAHs), Hg and As were used as a simplified model matrix and treated to simulate a real case study. A total PAHs removal efficiency of 57% was reached after 96 h of treatment under 0.05 V cm-1. Then, real polluted marine sediments from Augusta Bay (Syracuse) and Bagnoli-Coroglio Bay (Naples) in the southern Italy were treated as real contaminated sediments to be restored, to validate the proposed approach for real cases. A quite good removal efficiency of PAHs was reached after 96 h of electrochemical treatment coupled with a low energetic consumption due to the rather E values adopted. In addition, it was observed that this approach, under the adopted conditions, is unsuitable for the remediation of Hg and As.

A chemical remediation technique for a nearly-total removal of arsenic and mercury from contaminated marine sediments.

After decades of industrial exploitation of the coast and consequent contamination of the sites and marine sediments, it became essential to recover the marine ecosystem by remediation methods to remove toxic contaminants. In this work, a remediation method was developed to clean marine sediments contaminated by arsenic (As) and mercury (Hg). The method can be applied to mobile platforms and is based on an environmentally friendly approach designed to minimise further contamination. The method was tested on two artificially contaminated sediments and two real samples collected from two highly contaminated sites in southern Italy, Augusta Bay and Bagnoli Gulf, characterised by high Hg and As concentrations, respectively. The method consists of four steps: washing with sodium hydroxide (NaOH) to remove metals associated with humic acid; Fenton-reaction using α-CycloDextrin (aCD) to stabilise Fe(II) at natural pH and oxidise As (III) and Hg (0 or I); complexation reaction with aCD; and complexation with sodium sulfide (Na2S) to remove Hg as soluble Hg-polysulfides. Compared to other remediation experiences in literature, this technique provides the best removal efficiency for As and Hg (ranging between 26 -71 % and 57-95 %, respectively). Considering the residual concentrations of As and Hg and the contamination threshold fixed by European Regulation for re-use, the treated sediment can be used in several civil and industrial contexts. The presented method operates in line with the principles of the circular economy to preserve natural resources, prevent secondary pollution, and promote the effective re-use of clean environmental matrices (soils, sediments and aqueous solutions), thus minimising landfill waste.

An integrated approach to characterize deep sediment toxicity in Genoa submarine canyons (NW Mediterranean).

The aim of this study was to evaluate deep sediment toxicity in Genoa submarine canyons (Northwestern Mediterranean), for the first time, by using an integrated approach that combined chemistry and ecotoxicology. Sediments were collected from the main submarine canyons in the Gulf of Genoa (Polcevera and Bisagno) and along the adjacent Western Open Slope. A multi-endpoint ecotoxicological approach was taken by exposing two crustacean larvae (Amphibalanus amphitrite and Artemia sp.). Lethal and sub-lethal responses (mortality, swimming behavior) were investigated. Chemical analysis showed that this area is characterized by metal enrichment, including lead, cadmium, chromium, and nickel. Ecotoxicological tests highlighted that elutriates from the different submarine canyons were toxic only for A. amphitrite nauplii: Polcevera Canyon and Western Open Slope sediments induced stronger lethal and sub-lethal ecotoxicological effects than those from Bisagno Canyon. No direct correlation was found between the outcome of chemical and ecotoxicological characterization. However, barnacle was the most prone species to metal contamination: lethal and sub-lethal responses found in this species may be linked to an increase in the concentration of some metals (i.e., Cr, Ni) from offshore to coastal waters, probably due to anthropogenic activity. These findings suggest that the proposed approach can be a suitable tool for deep-sea sediment contamination monitoring; however, the use of a battery of bioassays involving multiple species and endpoints is recommended to better clarify the dynamics of contaminants in marine sediments at very high depths.

Heavy Metals and PAHs in Meat, Milk, and Seafood From Augusta Area (Southern Italy): Contamination Levels, Dietary Intake, and Human Exposure Assessment.

Heavy metals and PAHs were measured in animal foodstuffs from Augusta-Melilli-Priolo area in order to evaluate the potential human health risk associated to their consumption. All heavy metals were detected in seafood products while most of them were 1 for baby, children and teenagers, indicating a non-carcinogenic risk for these age categories by seafood ingestion. The CRAs overcame 1*10-5 for almost age categories (except "baby") and for elderly, by seafood and beef ingestions respectively. Moreover, the MOE for PAHs showed a certain cancer risk for "baby" related to cow milk ingestion.

Pathways of inorganic and organic contaminants from land to deep sea: The case study of the Gulf of Cagliari (W Tyrrhenian Sea).

In continental margins, canyons appear to act as natural conduits of sediments and organic matter from the shelf to deep basins, providing an efficient physical pathway for transport and accumulation of particles with their associated land-produced contaminants. However, these mechanisms have not been yet sufficiently explored by geochemical markers. The continental slope of the south Sardinia has been used as a natural laboratory for investigating mechanisms and times of transfer dynamics of contaminants from land to sea and from shelf to deep sea through an articulated system of submarine canyons. Here, dynamics of contaminants have been investigated in a pilot area of the central Mediterranean basin (Gulf of Cagliari, S Sardinia) where important industrial plants are sited since beginning of the last century. Five sediment cores dated by 210Pb and 137Cs reveal: i) a complex dynamics of organic and inorganic contaminants from point source areas on land to the deep sea and ii) a crucial role played by canyons and bottom morphology as primary pathway conveying sediments and associated contaminants from sources to very far deep sea environments. In particular, this study provides new integrated tools to properly understand mechanisms of connection between coastal sectors and deep sea. This is challenging mostly in regions where coastal pollution could represent critical threats for larger areas of the Mediterranean Sea.

Synthesis of water suitable as the MEPC.174(58) G8 influent water for testing ballast water management systems.

Here, we describe the methodologies adopted to ensure that natural seawater, used as "influent water" for the land test, complies with the requirement that should be fulfilled to show the efficacy of the new ballast water treatment system (BWTS). The new BWTS was located on the coast of SW Sicily (Italy), and the sampled seawater showed that bacteria and plankton were two orders of magnitude lower than requested. Integrated approaches for preparation of massive cultures of bacteria (Alcanivorax borkumensis and Marinobacter hydrocarbonoclasticus), algae (Tetraselmis suecica), rotifers (Brachionus plicatilis), and crustaceans (Artemia salina) suitable to ensure that 200 m(3) of water fulfilled the international guidelines of MEPC.174(58)G8 are here described. These methodologies allowed us to prepare the "influent water" in good agreement with guidelines and without specific problems arising from natural conditions (seasons, weather, etc.) which significantly affect the concentrations of organisms at sea. This approach also offered the chance to reliably run land tests once every two weeks.