10-year time course of Hg and organic compounds in Augusta Bay: Bioavailability and biological effects in marine organisms.

In the last century, many Mediterranean coastal areas have been subjected to anthropogenic disturbances from industrial activities, uncontrolled landfills, shipyards, and high maritime traffic. The Augusta Bay (eastern Sicily, Italy) represents an example of a strongly impacted coastal environment with an elevated level of sediments contamination due to the presence of one of the largest European petrochemical plants, combined with an extensive commercial and military harbor. The most significant contaminants were represented by mercury (Hg) and hexachlorobenzene (HCB), derived from a former chlor-alkali plant, and other organic compounds like polycyclic aromatic hydrocarbons (PAHs) and polychlorobiphenyls (PCBs). Since the 1970s, Augusta Bay has become internationally recognized as a contaminated marine environment, although very little information is available regarding the temporal trend of contaminants bioavailability and biological impacts on aquatic organisms. In this study, the Hg and HCB concentrations were investigated over 10 years (from 2003 to 2013) in sediments and invertebrate and vertebrate organisms; these two contaminants' ecotoxicity was further evaluated at a biochemical and cellular level by analyzing the induction of organic biotransformation processes and DNA damages. The results showed high concentrations of Hg and HCB in sediments and their strong bioaccumulation in different species with significantly higher values than those measured in reference sites. This trend was paralleled by increased micronuclei frequency (DNA damage biomarker) and activity of the biotransformation system. While levels of chemicals in sediments remained elevated during the time course, their bioavailability and biological effects showed a gradual decrease after 2003, when the chlor-alkali plant was closed. Environmental persistence of Hg and HCB availability facilitates their bioaccumulation and affects the health status of marine organisms, with possible implications for environmental risk, pollutants transfer, and human health.

Large-Scale Mercury Dispersion at Sea: Modelling a Multi-Hazard Case Study from Augusta Bay (Central Mediterranean Sea).

This contribution discusses an example of potential multi-hazard effects resulting from an earthquake in a highly seismogenic area of the Mediterranean Sea, the Augusta Bay, which presents high levels of contamination in sediments and seawater, due particularly to high-concentrations of mercury as a result of a long-term industrial exploitation. In particular, a high-resolution hydrodynamic and transport model is used to calculate the effects of enhanced mercury spreading in the open sea after significant damage and collapse of the artificial damming system confining the embayment where a very high concentration of Hg occurs in seafloor sediments and seawater. Coupling high-resolution 3D dynamic circulation modelling and sediment-seawater Hg fluxes calculated using the HR3DHG diffusion-reaction model for both inorganic and organic Hg species offers a valuable approach to simulating and estimating the effects of spatial dispersion of this contaminant due to unpredictable hazard events in coastal systems, with the potential attendant enhanced effects on the marine ecosystem. The simulated scenario definitely suggests that a combination of natural and anthropogenic multi-hazards calls for a thorough re-thinking of risk management in marine areas characterised by significant levels of contamination and where a deep understanding of the biogeochemical dynamics of pollutants does not cover all the aspects of danger for the environment.

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.

Pharmaceuticals and other contaminants in waters and sediments from Augusta Bay (southern Italy).

The contamination by pharmaceuticals products (PPs) in the marine environment is particularly relevant where wastewater treatment of urban areas on land is lacking. However, the number of studies focused on description of sources and fate of PP molecules in the marine environment remains still limited. In this study, the occurrence of 46 PPs was investigated in the marine and coastal-marine system (waters and sediments) of Augusta Bay (central Mediterranean Sea). This area is highly affected by industrial pollution and urban discharges (without wastewater treatment) and thus represents a 'natural laboratory' for exploring dynamics of multi-mixture contaminants in the marine environment. The study area is also part of the sub-region 'Central Mediterranean Sea' of the Marine Strategy Framework Directive and therefore offers an important reference site for exploring the distribution modes of PPs in the central Mediterranean Sea. In this work, samples of seawater, sediment, untreated wastewater, and marine receiving water were analysed using mass spectrometry with a target analysis for PPs and a suspect screening analysis for the presence of other contaminants. PPs concentration ranges were: 2426-67,155 ng/L for untreated wastewaters, 550-27,889 ng/L for marine receiving waters and 12-281 ng/L for seawaters. The highest concentrations were measured for the antibiotics, anti-inflammatories, cardiovascular and antihypertensive therapeutic classes. Likewise, sediments collected from untreated wastewater sewers resulted more contaminated. Ionic, non-ionic surfactants and personal care products were the most abundant compounds found in waters and sediments by suspect screening analysis. The risk associated with PPs contamination for aquatic organisms was relatively high in samples of marine receiving waters of the bay (with a risk quotient value up to 33,599). The levels of PPs in seawater and sediment compartments were generally not hazardous (RQ < 0.01), except for estrone with a calculated RQ = 2775.

Bioaccumulation of heavy metals in fish, crustaceans, molluscs and echinoderms from the Tuscany coast.

The concentration of As, Cd, Cr, Cu, Hg, Ni, Pb and Zn were analyzed in the edible part of several species of fish, crustaceans, molluscs and echinoderms collected in sensitive areas of the Tuscany coast (northern Italy). The concentration of As (0.39-78.1 µg g-1) and Hg (0.01-1.56 µg g-1) resulted in most cases higher than reference thresholds. Target hazard quotient (THQ) and lifetime cancer risk (TR) indexes were calculated to assess cancer and non-cancer risk due to oral exposure; the highest THQ values referred to As and Hg, with values ≥ 1 in 39% and 48% of cases, respectively. Total target hazard quotients (TTHQ) values suggested that the local population could experience adverse health effects due to consumption of local seafood, mainly of demersal and benthic species. Cancer risk was mainly associated with As exposure, and with Cd intake, especially through molluscs consumption. The NMDS model highlighted species specific bioaccumulation processes and specific sensitivity of species to different bioavailable heavy metals. Specifically, Mullus spp. and Scorpaena porcus preferentially accumulate Hg and Cr, Octopus vulgaris specimens were discriminated by the presence of Pb and Zn, while an evident preference for Cd and Cu was recorded in Squilla mantis. In addition, the distribution of heavy metals in organisms revealed sound differences between Follonica and Livorno sampling sites, demonstrating a highly heterogeneous anthropogenic impact in terms of heavy metals input from the industrial activity resting on land.

Marine pollution in the Libyan coastal area: Environmental and risk assessment.

A comprehensive assessment of the potential adverse effects on environment and human health generated by the inputs of chemicals from the most important Libyan petrochemical plant is presented. Ecotoxicological risk associated with the presence of As, Hg, Ni, Zn and PAHs in marine sediments is low or moderate, with a probability of toxicity for ecosystem <9% and <20% for heavy metals and PAHs respectively. However, surface sediments result strongly enriched in Hg and As of anthropogenic origin. Investigation of metals in fish allowed to assess potential risks for human populations via fish intake. Target hazard quotients values indicate potential risk associated to toxic metals exposure by fish consumption and lifetime cancer risk (TR) values highlight a potential carcinogen risk associated to As intake. Noteworthy, the presented results provide an unprecedented environmental dataset in an area where the availability of field data is very scant, for a better understanding of anthropogenic impacts at Mediterranean scale.

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.