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.

The key role played by the Augusta basin (southern Italy) in the mercury contamination of the Mediterranean Sea.

The Augusta basin, located in SE Sicily (southern Italy), is a semi-enclosed marine area, labelled as a highly contaminated site. The release of mercury into the harbour seawater and its dispersion to the blue water, make the Augusta basin a potential source of anthropogenic pollution for the Mediterranean Sea. A mass balance was implemented to calculate the HgT budget in the Augusta basin. Results suggest that an average of ∼0.073 kmol of HgT is released, by diffusion, on a yearly basis, from sediments to the seawater, with a consequent output of 0.162 kmol y(-1) to coastal and offshore waters; this makes the Augusta area an important contributor of mercury to the Mediterranean Sea. Owing to the geographical location of the Augusta basin, its outflowing shelf-waters are immediately intercepted by the surface Atlantic Ionian Stream (AIS) and mixed with the main gyres of the eastern Mediterranean Sea, thus representing a risk for the large-scale marine system.

Organochlorines and Polycyclic Aromatic Hydrocarbons as fingerprint of exposure pathways from marine sediments to biota.

To elucidate the dynamics of a suite of organochlorine contaminants (PCBs, HCB), PAHs and Hg and verify the potential of these pollutants as reliable fingerprints of sources, an ensemble of marine sediments and organisms (finfish, shellfish species and Mytilus galloprovincialis) were analysed from the contaminated Augusta Bay (Southern Italy). The Hg and HCB concentration in the sediments exceeded the EQS of the Directive 2000/60/EU. Similarly, ∑PCB and selected PAHs were above the threshold limit set by regulation. The marine organisms showed Hg concentrations above CE 1881/2006. Contaminants in transplanted mussel evidenced an increased accumulation overtime and different distribution patterns between sampling sites. Analysis of the homolog composition of PCB congeners revealed comparable patterns between sediments and marine organisms and offered the opportunity to define a robust fingerprint for tracing contaminants transfer from the abiotic to the biotic compartments. These results were confirmed by the Fluoranthene/Pyrene, Hg and HCB distribution modes.

Dataset for the assessment of selected POP's pollution and effectiveness of environmental policies in the Bac Giang Province and Cau River (Northern Vietnam).

This data article presents the datasets obtained during the years 2011-2012 in the Provinces of Bac Giang and Bac Ninh (Northern Vietnam) in the framework of an International Cooperation project aimed at the restoration and preservation of natural resources together with the improvement of life conditions of the local population. All information relative to sampling strategy, location and description of the studied sites are reported, together with analytical data (i.e. grain size, Total Organic Carbon, Organic Nitrogen, C/N ratio, δ13C, PolyChlorinated Biphenyls, Polycyclic Aromatic Hydrocarbons, PolyBrominated Diphenyls Ethers, PolyChlorinated Dibenzo-p-Dioxins and Furans, OrganoChlorine Pesticides, Total Petroleum Hydrocarbons). In addition, maximum admitted levels, quality standards and emission limits set by the Vietnamese environmental regulations are reported in comparison to Italian ones for the following parameters and environmental compartments: noise, soils, air, drinking and groundwaters, sediments. Interpretation of this dataset is fully discussed in Giuliani et al. (2019) [1].

Benthic Foraminifera as bio-indicators of anthropogenic impacts in coastal environments: Acqua dei Corsari area case study (Palermo, Italy).

This study investigates living benthic foraminiferal assemblages as bio-indicators of anthropogenic activities in a coastal area within the Gulf of Palermo (Sicily, Italy), affected by industrial and urban activities, and evaluates the environmental quality through the calibration of a Tolerant Species index (%TSstd). Sediments from 6 stations were sampled along a bathymetric transect from the coast to offshore. Sediment grain size, TOC, major, minor and trace elements and polycyclic aromatic hydrocarbons (PAHs) were compared to benthic foraminiferal assemblages and species at each station. Diversity and density of benthic foraminiferal assemblages were not affected by the presence of pollutants, while tolerant species increased with organic (TOC and PAHs) or chemical (As and Pb) concentrations. Moreover, the calibration of the %TSstd formula to >125µm foraminiferal assemblage, gives a detailed description of environmental quality along the transect, representing a good and sensitive tool to evaluate marine coastal environment.

Mercury levels in sediments of central Mediterranean Sea: a 150+ year record from box-cores recovered in the Strait of Sicily.

To evaluate the degree of anthropogenic mercury pollution, Hg contents have been measured for box-core sediments sampled along three nearshore-offshore transects in the Strait of Sicily and well constrained for their mineralogy, bulk geochemistry and TOC%. Hg values are generally low (from 15 to 70 microg kg(-1)); however, depth profiles clearly display upcore rising concentrations (up to 202 microg kg(-1) near the SE Sicily coast) that are attributed to anthropogenic load. Based on (210)Pb chronology, these trends are more dramatic across the last 20-30 years. Geogenic influence is thought to explain some anomalies related to volcanic emission and geothermal activity. Combined effects due to eastward flowing of the Modified Atlantic Water (MAW) and sea bottom morphology drove major anthropogenic accumulation.

Mediterranean circulation perturbations over the last five centuries: Relevance to past Eastern Mediterranean Transient-type events.

The Eastern Mediterranean Transient (EMT) occurred in the Aegean Sea from 1988 to 1995 and is the most significant intermediate-to-deep Mediterranean overturning perturbation reported by instrumental records. The EMT was likely caused by accumulation of high salinity waters in the Levantine and enhanced heat loss in the Aegean Sea, coupled with surface water freshening in the Sicily Channel. It is still unknown whether similar transients occurred in the past and, if so, what their forcing processes were. In this study, sediments from the Sicily Channel document surface water freshening (SCFR) at 1910 ± 12, 1812 ± 18, 1725 ± 25 and 1580 ± 30 CE. A regional ocean hindcast links SCFR to enhanced deep-water production and in turn to strengthened Mediterranean thermohaline circulation. Independent evidence collected in the Aegean Sea supports this reconstruction, showing that enhanced bottom water ventilation in the Eastern Mediterranean was associated with each SCFR event. Comparison between the records and multi-decadal atmospheric circulation patterns and climatic external forcings indicates that Mediterranean circulation destabilisation occurs during positive North Atlantic Oscillation (NAO) and negative Atlantic Multidecadal Oscillation (AMO) phases, reduced solar activity and strong tropical volcanic eruptions. They may have recurrently produced favourable deep-water formation conditions, both increasing salinity and reducing temperature on multi-decadal time scales.

Distribution of REEs in box-core sediments offshore an industrial area in SE Sicily, Ionian Sea: evidence of anomalous sedimentary inputs.

The distribution of rare earth elements and yttrium (REEs+Y) has been investigated in box-core sediments recovered from four stations in the Sicilian coastal zone seawards of Augusta, one of the most industrialized and contaminated areas in the Mediterranean region. Shale-like REE patterns and low Y/Ho ratios (close to the chondritic ratio) suggest a dominant terrigenous (geogenic) source for REE. Slight enrichment of LREE over the HREE is interpreted as due to preferential adsorptive transfer of LREE from seawater to sediment particles. Samples from offshore cores exhibit slightly positive Gd and negative Ce anomalies. It is here hypothesized that main drivers of anthropogenic Gd flux towards the offshore are dredged contaminated materials that, recovered from the Augusta Bay, have been repeatedly discharged offshore. Consistent with the redox-chemistry of Ce, these anomalous sedimentary inputs induce a decrease of O(2) concentration in the sediment, which in turn triggers Ce regeneration.