Mobility of heavy metals from polluted sediments of a semi-enclosed basin: in situ benthic chamber experiments in Taranto’s Mar Piccolo (Ionian Sea,Southern Italy)

In situ benthic flux experiments were conducted at two stations in the Mar Piccolo of Taranto (Italy), one of the most industrialised and contaminated coastal areas of the Mediterranean. Sediments of the two stations are notably different in their trace metal content, with a station closer to a Navy harbour showing higher mean concentrations of almost all investigated metals (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn). Conversely, both stations are characterised by significant Hg contamination, compared to the local baseline. Results of a sequential extraction scheme on surface sediments suggest a relatively scarce mobility of the examined metals (Zn > Ni > Cr > As > Cu > Pb). A Hg-specific extraction procedure showed that most of the element (93.1 %) occurs in a fraction comprising Hg bound to Fe/Mn oxi-hydroxides. Reduction of these oxides may affect Hg remobilisation and redistribution. Porewater profiles of dissolved trace metals were quite similar in the two sites, although significant differences could be observed for Al, Cu, Fe and Hg. The highest diffusive fluxes were observed for As, Fe and Mn. Mobility rates of several trace elements (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn) were directly measured at the sediment–water interface. Results from benthic in situ incubation experiments showed increasing dissolved metal concentrations with time, resulting in higher fluxes for Cu, Fe, Hg, V and Zn in the most contaminated site. Conversely, fluxes of Mn, Ni and Pb were comparable between the two stations. The estimated flux of Hg (97 μg m^?2 day^?1) was the highest observed among similar experiments conducted in other highly contaminated Mediterranean coastal environments. Benthic fluxes could be partially explained by considering rates of organic matter remineralisation, dissolution of Fe/Mn oxy-hydroxides and metal speciation in sediments. Seasonal and spatial variation of biogeochemical parameters can influence metal remobilisation in the Mar Piccolo area. In particular, metals could be promptly remobilised as a consequence of oxygen depletion, posing a serious concern for the widespread fishing and mussel farming activities in the area.     

Accumulation and tissue distribution of mercury and selenium in striped dolphins (Stenella coeruleoalba) from the Mediterranean Sea (southern Italy).

Tissues and organs from Stenella coeruleoalba stranded along the Apulian coasts (southern Italy) during the period April-July 1991 were analyzed for their mercury and selenium content. Analysis showed considerable variations in the mercury concentration in the examined organs and tissues. The highest concentrations of mercury were found in the liver (from 2.27 to 374.50 microg g(-1) wet wt.). After the liver, lung, kidney, muscle and brain were the most contaminated, while the lowest mercury contamination was found in the melon. As mercury, the liver also showed the highest selenium levels. Liver samples were also analyzed for their methyl mercury contents. The role of selenium in detoxification process of methyl mercury has been discussed. Mercury concentrations related to geographic variations and pollution of the marine environment have been examined. The possible implications between mercury accumulation and dolphin death have also been discussed.     

Metals and PCB levels in some edible marine organisms from the Ionian Sea: dietary intake evaluation and risk for consumers

Concentrations of some metals (Cd, Cu, As, Hg, Pb) and polychlorinated biphenyls (PCBs) were investigated in edible marine organisms from different trophic levels and feeding behaviour like bivalve molluscs (Mytilus galloprovincialis and Chlamys glabra), gastropod molluscs (Hexaplex trunculus) and some commercial species of fish (Trachurus trachurus, Boops boops, Sarpa salpa and Gobius niger). These species were collected in the first inlet of the Mar Piccolo of Taranto (Ionian Sea, Southern Italy), classified as ‘Site of National Interest’ established by National Law 426 (1998) and included in the ‘National Environmental Remediation and Restoration Projects’. The aim of this work was to investigate contamination levels and public health risks, associated with consuming seafood harvested from these areas. Moreover, in this study, was also estimated the weekly intake in children and adults, both for metals and PCBs. In comparison with the permissible limits set by EC Regulations, Cd and Pb levels were over the limit in the H. trunculus (in all sampling stations) and in the fish T. trachurus respectively. PCBs were over the legal limit in all sampled species with the exception of M. galloprovincialis (station 1), C. glabra and the herbivorous fish S. salpa. In the fish T. trachurus, for example, the concentration of six target PCBs was about five times higher than the EC limit. The estimated intakes of those trace elements included in this study through seafood consumption by the population exceed the provisional tolerable weekly intake recommended by the Joint FAO/WHO Expert Committee on Food Additives for Cd and Hg in the H. trunculus and T. trachurus, especially in children. Moreover, hazard quotience (HQ) for Hg and Cd was >1 in the children for T. trachurus and H. trunculus consumption. As regard non-dioxin-like PCB (NDL-PCB), the estimated intake were always above the ‘provisional guidance value’ (70 ng/kg body weight) Arnich et al. (Regul Toxicol Pharm 54: 287–2, 2009) for all sampled organism. Thus, health risks due to the dietary Hg, Cd and PCBs intake, especially for children, cannot be excluded. Therefore, an extended remediation programme is necessary to safeguard marine ecosystem, human health and, not less important, the economic activities, in the Taranto marine area.     

The Mar Piccolo of Taranto: an interesting marine ecosystem for the environmental problems studies

The National Project RITMARE (la Ricerca ITaliana per il MARE—Italian Research for the sea) started from 1 January 2012. It is one of the national research programs funded by the Italian Ministry of University and Research. RITMARE is coordinated by the National Research Council (CNR) and involves an integrated effort of most of the scientific community working on marine and maritime issues. Within the project, different marine study areas of strategic importance for the Mediterranean have been identified: Among these, the coastal area of Taranto (Ionian Sea, Southern Italy) was chosen for its different industry settlements and the relative impact on the marine environment. In particular, the research has been concentrated on the Mar Piccolo of Taranto, a complex marine ecosystem model important in terms of ecological, social, and economic activities for the presence also of extensive mussel farms. The site has been selected also because the Mar Piccolo area is a characteristic “on field” laboratory suitable to investigate release and diffusion mechanisms of contaminants, evaluate chemical–ecological risks towards the marine ecosystem and human health, and suggest and test potential remediation strategies for contaminated sediments. In this context, within the project RITMARE, a task force of researchers has contributed to elaboration a functioning conceptual model with a multidisciplinary approach useful to identify anthropogenic forcings, its impacts, and solutions of environmental remediation. This paper describes in brief some of the environmental issues related to the Mar Piccolo basin.     

Metal distribution in marine sediments of the Mar Piccolo in Taranto (Ionic Sea,southern Italy)

The spatial distribution of selected metals (Fe, Ni, Mn, Zn, Cu, Pb, Hg and Cd) and their partition in the different chemical forms (speciation) were determined in benthic sediments from Mar Piccolo, Taranto (Ionic Sea, southern Italy). The aim of this study was to assess the degree of sediment contamination and bioavailability of metals, very important for Italian mussel culture, in a semi-enclosed marine ecosystem. In sediments, grain size distribution, total organic carbon (TOC), and humic (HA) and fulvic (FA) acids contents were also determined. The compounds TOC, HA and FA, in fact, have a great influence on metal complexation. High concentrations of copper, lead, zinc and mercury were found, especially in sediments of the first inlet of Mar Piccolo. Statistical analysis of results shows significant correlation among Cu, Pb and Zn concentrations and the influence of organic matter on the sediment distribution of Cu, Pb and Zn. Metal speciation analysis, carried out with sequential extraction method, shows that Fe and Ni are present in sediments mainly as sulphides. Mn and Pb are present principally in an ion-exchangeable form or bound to carbonate and Cu is associated to organic matter. Metal pollution index (MPI), calculated as a weighed mean of the metal contamination factors in each station, shows that with regard to Cu, Ni, Pb and Zn, some stations investigated are unpolluted (MPI <1), whereas in other areas, pollution level is not very high. On the contrary, for mercury, the pollution level in the first inlet of the basin is very high.     

Methodological approach for metal pollution evaluation in sediments collected from the Taranto Gulf

The concentrations of Hg, Cd, Pb, Cu, Ni, V, and Sn were determined in marine sediments collected from Taranto Gulf (Ionian Sea, Southern Italy). The aim of this article is to study the methodological approach in order to evaluate total metal levels determined in marine sediments of a contaminated area (Taranto Gulf, Southern Italy), to identify contaminated areas and to predict adverse biological effects based on Sediment Quality Guidelines (SQGs). The results are discussed in relation to geological characteristics of sediments in order to define background levels and anthropogenic input. Experimental results were elaborated by multivariate statistical techniques and Geographical Information System (GIS) software. The geoaccumulation index I _geo and two sets of SQGs (in particular (a) the threshold effect level (TEL), the probable effect level (PEL) and (b) the effect range-low (ERL) and the effect range median (ERM)) have been used for environmental evaluation of metal concentrations. Results show that in Taranto coastal area, Mar Piccolo basin represents the most contaminated area. A comparison with results from other Mediterranean areas demonstrates that for some metals (such as Cd, Pb, and Hg) Taranto seas represent one of the most polluted areas in the Mediterranean Sea. A comparison of metal levels with SQGs also suggests an ecotoxicological risk for benthic organisms mainly in the first inlet of Mar Piccolo.     

Association of metals (mercury, cadmium and zinc) with metallothionein-like proteins in storage organs of stranded dolphins from the Mediterranean sea (Southern Italy)

Selected toxic and essential metals (mercury, Hg; cadmium, Cd; and zinc, Zn) were determined in the liver and in the kidney collected from 13 dolphins (Stenella coeruleoalba and Tursiops truncatus) stranded along the southern coasts of Italy from 1991 to 1999. Liver samples were also analysed for their methyl mercury (MeHg) and selenium (Se) contents. For subcellular fractionation, liver and kidney samples were homogenized in Tris-HCl buffer; after centrifugation, the supernatant (cytosol) was separated from pellets (insoluble fraction), heated at 80 degrees C for 10 min and centrifuged in order to separate the precipitate containing the thermolabile high molecular weight proteins. The cytosol heat-stable fraction, including metallothionein-like proteins (MTLPs), was then purified by gel filtration chromatography on Sephadex G-75 column. The three subcellular fractions collected (insoluble fraction, thermolabile fraction and purified heat-stable fraction) were analysed for their Hg, Cd and Zn contents. The analytical results confirm previous similar studies on toothed whales in showing that: (1) in the liver, as well as in the kidney, Hg was mainly found in the insoluble fraction, therefore, metallothioneins seem to have no role in the Hg detoxification; (2) in the liver, the molar ratio between Se and inorganic Hg was very close to 1; this suggests that the final compound of MeHg detoxification could be HgSe (tiemannite); (3) in almost all the samples, Cd and Zn were detected in the purified heat-stable fraction (including MTLPs). The mechanism of Cd detoxification and Zn homeostasis is also discussed.     

Metal distribution in sediments from the Adriatic Sea

Total metal concentrations (Cu, Ni, Pb, Zn, Fe, and Mn) and their distribution in different chemical forms (speciation) were determined in sediments from the Adriatic Sea in order to evaluate contamination and mobility of metals. The study was carried out on marine sediments collected in two areas of the Adriatic Sea differently influenced by Po river waters. Metal distribution in the study area depends prevalently on water circulation and on organic matter distribution. Among metal levels, significant correlations between copper and zinc and between lead and nickel were found, suggesting common and specific sources. As regards metal speciation, the distribution of different chemical forms changes with the metal. The prevailing zinc phases, for example mobile forms, and sulphide together are greater than 50% of total metal. Nickel is mainly present in sediments as sulphide, and the preferential association of copper with organic matter is evident. Lead and manganese are preferentially found as mobile forms (more of 30% for lead, 40% or more for manganese).     

Monitoring of PCDD/Fs and dioxin-like PCBs and seasonal variations in mussels from the Mar Grande and the Mar Piccolo of Taranto (Ionian Sea,Southern Italy)

The levels and specific profiles of polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in Mytilus galloprovincialis from the Mar Grande and the Mar Piccolo of Taranto were determined during the extensive monitoring plan of Local Health Authority to assess PCDD/Fs and DL-PCBs contamination in food and farm products, within 20 km from the industrial areas of Taranto, between March and December 2011. The average Total Toxicity Equivalence (TEQ) values for the sum of PCDD/F and DL-PCBs ranged from 1.61 to 5.63 pg WHO₂₀₀₅-TEQ g^?1 wet weight basis, with the highest in the first inlet of the Mar Piccolo. In particular, DL-PCBs were the dominant chemicals in all samples, followed by PCDFs and PCDDs. Congener patterns in mussels were similar, indicating a homogeneous behavior in studied areas and, probably, the same type of source. The seasonal concentrations trend showed a relevant increase of dioxin and dioxin-like PCBs TEQs during the summer months, exceeding the limits set by the European Community for food and foodstuff. Reducing PCDD/Fs and PCBs is necessary to decrease contamination levels in order to safeguard marine ecosystem and human health in the Taranto area.