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

[This corrects the article DOI: 10.3389/fpubh.2022.968296.].

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.

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.

The marine sedimentary record of natural and anthropogenic contribution from the Sulcis-Iglesiente mining district (Sardinia, Italy).

Intensive exploitation of base metal deposits in the Sulcis-Iglesiente district (Sardinia, Italy), lasted from the 1850s to the 1990s, determined a high environmental impact on the coastal area, but the effects on marine environment have never been investigated. A marine sediment core, dated with 14C, was characterized for grain size, chemical and mineralogical composition, in order to reconstruct the sedimentary history of the area and to assess the environmental impact of mining. The comparison of chemical and mineralogical characteristics of recent sediments with those of pre-industrial age allowed discriminating the real anthropogenic impact from the natural metal enrichment. The correspondence, in the upper core, of anthropogenic trace metal enrichment with the presence of mine waste minerals is attributed to the exploiting over industrial scale; the still high metal enrichment in sediment surface levels suggests a still existing impact due to mine dumps and tailings weathering.

Evolution of the anthropogenic impact in the Augusta Harbor (Eastern Sicily, Italy) in the last decades: benthic foraminifera as indicators of environmental status.

The study of benthic foraminifera in sediment cores provides the opportunity to recognize environmental changes, including those due to the anthropogenic impact. The integration of these data with chemical-physical parameters provides a comprehensive quality assessment. This research was applied to a sediment core collected in the Augusta bay, where a very large commercial and military harbor and one of the largest petrochemical poles in Europe are present. Inside the petrochemical area also operated, from 1958 to 2003, a chlor-alkali plant with mercury cell technology which caused anthropic contamination of surrounding land and marine areas. The sediment core was collected in front of this plant and characterized for grain size and pollutants directly associated to chlor-alkali activity, such as mercury (Hg), barium (Ba), polychlorobiphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs). Composition of foraminiferal assemblages and faunal parameters such as specific diversity, faunal density, abundance of abnormal specimens, and foraminiferal size were investigated as potential indicators of environmental status. Statistical analysis indicated a main common origin for Hg, Ba, and PCBs and the influence of pollutants on species distribution and faunal diversity and density. Exceptionally high Hg concentrations (63-680 mg/kg d.w.) were recorded in the whole core, where the geochronological study attributed the most contaminated levels to the period of maximum activity of the chlor-alkali plant, while a decrease of contamination was recorded after the stop of the activity. Distinct foraminiferal assemblages identified different ecozones along the core, which suggested decreasing anthropogenic impact from the bottom to the top.

Establishing geochemical background levels of selected trace elements in areas having geochemical anomalies: The case study of the Orbetello lagoon (Tuscany, Italy).

The determination of background concentration values (BGVs) in areas, characterised by the presence of natural geochemical anomalies and anthropogenic impact, appears essential for a correct pollution assessment. For this purpose, it is necessary to establish a reliable method for determination of local BGVs. The case of the Orbetello lagoon, a geologically complex area characterized by Tertiary volcanism, is illustrated. The vertical concentration profiles of As, Cd, Cr, Cu, Hg, Ni, Pb and Zn were studied in four sediment cores. Local BGVs were determined considering exclusively samples not affected by anthropogenic influence, recognized by means of multivariate statistics and radiochronological dating ((137)Cs and (210)Pb). Results showed BGVs well-comparable with mean crustal or shale values for most of the considered elements except for Hg (0.87 mg/kg d.w.) and As (16.87 mg/kg d.w.), due to mineralization present in the catchment basin draining into the lagoon.

Sediment characterization of the highly impacted Augusta harbour (Sicily, Italy): modern benthic foraminifera in relation to grain-size and sediment geochemistry.

The Augusta harbour is affected by high anthropogenic impact due to intense harbour activity and a large chemical and petrochemical pole. Thirty-seven sediment samples were collected during an environmental characterization project and analyzed for grain size, chemical parameters (Al, As, Cd, Cr, Cu, Fe, Hg, Ni, Pb, Zn and V) and foraminifera, the last one generally being used as ecological indicators of environmental quality. Anthropogenic enrichment was recognized for As, Cu, Hg, Pb and Zn and, among these, Hg showed very high concentrations (up to 191 mg kg(-1) d.w.) often associated in the southern sector of the study area to very high PCB levels (up to 0.83 mg kg(-1)). In this area, an assemblage dominated by Rosalina bradyi and Quinqueloculina lata was recognized. This assemblage shows a clear decrease of foraminiferal density and diversity and, at the same time, increased dominance with respect to the assemblage characterizing the central and northern less polluted sectors, in which Miliolinella subrotunda prevails. Quinqueloculina lata was demonstrated to be a stress-tolerant species because it was not influenced by sediment texture, but positively correlated with the concentration of Hg, PCBs and PAHs. The environmental stress shown by the high-dominance of the Ammonia tepida assemblage was attributed mainly to the influence of stream mouths, which determine environmental instability. Foraminiferal assemblages showed a clear response to environmental degradation in the most polluted area but, at the same time, they demonstrated a high adaptation to pollution.

A multidisciplinary weight of evidence approach for classifying polluted sediments: Integrating sediment chemistry, bioavailability, biomarkers responses and bioassays.

Evaluation of chemical bioavailability and onset of biological alterations is fundamental to assess the hazard of environmental pollutants, particularly when associated to sediments which need to be removed. In the present work, five sediment samples were collected from the Venice Lagoon and data from sediment chemistry were integrated with those of bioaccumulation of chemicals in European eel (Anguilla anguilla) exposed under laboratory conditions, responses of a wide battery of biomarkers, and standardized ecotoxicological bioassays. The overall results were elaborated within a recently developed, software-assisted weight of evidence (WOE) model which provides synthetic indices for each of considered line of evidence (LOE), before a general evaluation of sediment hazard. Levels of chemicals in sediments were not particularly elevated when compared to sediment quality guidelines of Venice Protocol. On the other hand, bioavailability was evident in some samples for Cd, Cu, Zn and, especially, polycyclic aromatic hydrocarbons. The ecotoxicological approach provided further evidence on the biological and potentially harmful effects due to released contaminants, and oxidative-mediated responses appeared of primary importance in modulating sublethal responses and the onset of cellular alterations. Biomarkers variations were sensitive, and more evident variations included significant changes of cytochrome P450 biotransformation pathway, antioxidant responses, onset of oxidative damages, lysosomal membrane stability and genotoxic effects. The results obtained from the battery of bioassays indicated that responses measured at organism level were in general accordance but less marked compared to the onset of sublethal changes measured through biomarkers. Overall this study revealed differences when comparing evaluations obtained from different LOEs, confirming the importance of considering synergistic effects between chemicals in complex mixtures. Compared to a qualitative pass-fail approach toward normative values, the proposed WOE model allowed a quantitative characterization of sediment hazard and a better discrimination of on the basis of various types of chemical and biological data.

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.

Assessing sediment hazard through a weight of evidence approach with bioindicator organisms: a practical model to elaborate data from sediment chemistry, bioavailability, biomarkers and ecotoxicological bioassays.

Quality assessments are crucial to all activities related to removal and management of sediments. Following a multidisciplinary, weight of evidence approach, a new model is presented here for comprehensive assessment of hazards associated to polluted sediments. The lines of evidence considered were sediment chemistry, assessment of bioavailability, sub-lethal effects on biomarkers, and ecotoxicological bioassays. A conceptual and software-assisted model was developed with logical flow-charts elaborating results from each line of evidence on the basis of several chemical and biological parameters, normative guidelines or scientific evidence; the data are thus summarized into four specific synthetic indices, before their integration into an overall sediment hazard evaluation. This model was validated using European eels (Anguilla anguilla) as the bioindicator species, exposed under laboratory conditions to sediments from an industrial site, and caged under field conditions in two harbour areas. The concentrations of aliphatic hydrocarbons, polycyclic aromatic hydrocarbons and trace metals were much higher in the industrial compared to harbour sediments, and accordingly the bioaccumulation in liver and gills of exposed eels showed marked differences between conditions seen. Among biomarkers, significant variations were observed for cytochrome P450-related responses, oxidative stress biomarkers, lysosomal stability and genotoxic effects; the overall elaboration of these data, as those of standard ecotoxicological bioassays with bacteria, algae and copepods, confirmed a higher level of biological hazard for industrial sediments. Based on comparisons with expert judgment, the model presented efficiently discriminates between the various conditions, both as individual modules and as an integrated final evaluation, and it appears to be a powerful tool to support more complex processes of environmental risk assessment.

The impact of the Bagnoli industrial site (Naples, Italy) on sea-bottom environment. Chemical and textural features of sediments and the related response of benthic foraminifera.

The coastal zone of the disused industrial site of Bagnoli, has been studied since 1999 in order to highlight chemical and ecological features of pollution, mainly due to a steel plant. This further study was performed in order to check the foraminiferal response to changes in sediment grain-size and contaminant concentrations and to recognise the actual effects of the environmental stress determined by industrial pollution on the foraminiferal assemblages. This was attained by considering a wider area than in the previous studies so as to recognise the possible reference conditions. Very high contamination, mainly due to Cu, Fe, Hg, Mn, Ni, Pb, Zn and PAHs, was recorded in the marine sediments close to the steel plant. Contaminant concentrations and sediment composition were recognised as important factors influencing the foraminiferal response by means of statistical analysis. The foraminiferal abnormality index (FAI) is positively correlated with heavy metals concentration, exceeding the natural threshold in front of the plant. Furthermore, increasing pollution levels correspond to the increase of pollution-tolerant species in the assemblage.

Benthic foraminifera from the coastal zone of Baia (Naples, Italy): assemblage distribution and modification as tools for environmental characterisation.

The coastal zone of Baia (Naples) is currently included in a protected marine area, but in past it was affected by strong anthropogenic pressure for commercial harbour activity. In order to investigate the impact of past activities, a multidisciplinary characterisation was undertaken to evaluate the environmental quality of marine sediments. Thirty-six grab samples were collected for grain-size, heavy metals, PAHs and PCBs analyses. Rose Bengal stained replicates were taken for the analysis of benthic foraminifera. Chemical analyses highlighted sediment pollution mainly due to Cu, Hg, Pb, Zn, PAHs and PCBs in the northern and southern part of the study area, where some sunken vessels had been present for many decades. Modifications of foraminiferal diversity and density, and increased percentage of abnormal specimens, were considered as indicators of environmental degradation. Correlation between faunal parameters and pollutant concentrations was found by means of statistical analysis. The highest degree of environmental stress shown by foraminifera in the northern sector could be referable to the high concentrations of PCBs (up to 144 ng g(-1) d.w.).

Ecotoxicological and human health risk in a petrochemical district of southern Italy.

An ecotoxicological investigation has been carried in the petrochemical district of Priolo (Sicily, Italy), one of the largest in Europe. Results indicated a severe mercury contamination in sediments sampled near a chloro-alkali plant. A clear bioavailability of this element was demonstrated in mussels Mytilus galloprovincialis (both native and translocated) and the benthic fish Mullus barbatus, which also exhibited marked genotoxic damages. The elevated mercury concentrations in marine organisms are a serious concern for human health; according to the national average fish consumption, the provisional tolerable weekly intake (PTWI) of Hg would be easily exceeded by at least 4 to 12 fold. Such toxicological risk is of particular importance for pregnant women, being possibly involved in the elevated frequency of neonatal malformations.

Industrial pollution at Bagnoli (Naples, Italy): benthic foraminifera as a tool in integrated programs of environmental characterisation.

In the 20th century an important industrial plant operated on the coastal area of Bagnoli. After its closing, an integrated study of environmental characterisation aimed at restoration started. The survey conducted was based on chemical and sedimentological analyses integrated with benthic foraminifera analyses. Statistical analysis of the data shows sectors with a distinct type and degree of pollution. Particularly, pollution linked to the silty sediment fraction, mainly due to Pb and Zn, was recognised in front of the southern sector of the plant. The study of benthic foraminifera provides evidence for a pollution-tolerant character in some species like Haynesina germanica and Quinqueloculina parvula. In addition, two species among the 113 recognised show high percentages of abnormal specimens. These percentages show a statistical correlation with some pollutants (PAHs, Mn, Pb and Zn). In addition, Energy Dispersive Spectrometry shows small amounts of Fe ions included in deformed tests of Miliolinella subrotunda. Because the number of these deformations is positively correlated to the concentration of PAHs, Mn and Zn, the inability of some specimens to exclude the foreign elements from the crystalline reticulum of the test could be attributed to the potential toxic effect of these pollutants.

Organochlorine compounds in tissues of swordfish (Xiphias gladius) from Mediterranean Sea and Azores islands.

Polychlorobiphenyls (PCB) and organochlorine (OC) pesticides are endocrine-disrupting chemicals (EDCs). The Italian Ministry of Environment has undertaken a program (1999-2001) to measure levels of contaminants in top marine predators and to develop sensitive biomarkers for the evaluation of toxicological risk in these species. In 1999, 15 swordfishes (Xiphias gladius) taken from the Mediterranean Sea along the Sicilian coast (Strait of Messina, Italy) and in the Atlantic Ocean along the Azores Islands, and analysed for 34 congeners of PCBs and 27 organochlorine (OC) pesticides in gonad, muscle, liver and blubber tissues. In the tissues of Mediterranean swordfishes the sum of the determined PCBs congeners ranged from 4.61 to 4651.17 ng g(-1) on fresh tissue basis. Among organochlorine pesticides DDE, DDT and DDD (TDE) predominated with an overall range of 2.37-4734.56 ng(-1) w.w. In particular p,p'-DDE had concentrations appearing up to 3900 ng(-1), with the highest values found in fatty tissues, such as blubber. In the liver of Azores Island swordfishes lower levels of summation PCBs (8.43-294.17 ng/g w.w.) and summation DDTs (<0.01-217.44 ng/g w.w.) were determined.

Marine sediment contamination of an industrial site at Port of Bagnoli, Gulf of Naples, Southern Italy.

For almost one century an important steel plant has been active at the Bagnoli industrial area (Naples, Southern Italy). The environmental survey of near shore and offshore sediments has been carried out as fundamental part of a clean up project. The characteristics of the area, supposed type of pollution, national and international protocols in force were taken into consideration in designing sampling schemes and selecting analytical parameters. For this work, sediment grain size, PAHs, PCBs, trace elements, total hydrocarbons and organic matter were considered. Factor analysis evidenced two main types of pollution in the proximity of the industrial plant, both probably attributable to the activity of the industrial site. The first one, due to Cd, Pb, Zn and Mn seems determined by localised activities at the southern part of the plant. The second one, due to Fe and Mn, appears directly linked to the whole contaminated area.

Evaluation of ecotoxicological effects of endocrine disrupters during a four-year survey of the Mediterranean population of swordfish (Xiphias gladius).

In this project we investigated the ecotoxicological effects of endocrine disrupters in a four-year survey of the Mediterranean population of swordfish (Xiphias gladius). In the Mediterranean environment, top predators, such as swordfish, accumulate high concentrations of polyhalogenated aromatic hydrocarbons (PHAHs) and toxic metals, potentially incurring high toxicological risk. The effects of organochlorines and trace elements (Hg, Cd and Pb) in 192 swordfish specimens, caught in the Strait of Messina, Sicily, Italy, were investigated using vitellogenin (Vtg), zona radiata proteins (Zrp) and CYP1A (BPMO, EROD) activities. Vtg and Zrp were found to be dramatically induced in some adult male specimens, suggesting that this species is highly exposed to estrogens in the Mediterranean Sea. A role of organochlorines in this induction phenomenon is suggested by the statistically significant correlations between Zrp in plasma and PCB concentrations in muscle (p<0.032) and Vtg in plasma and PCB concentrations in liver (p<0.034) of male specimens. Levels of trace elements in liver were in the following ranges: Hg 1-22, Cd 1-28 and Pb 0-1.6 ppm d.w. These data indicate potential reproductive alterations in large pelagic fish and suggest the need for continuous monitoring to avoid reductions in the population of this fish species of high commercial and ecological interest.