Imposex levels and butyltin compounds (BTs) in Hexaplex trunculus (Linnaeus, 1758) from the northern Adriatic Sea (Italy): Ecological risk assessment before and after the ban.

The aim of this study was to compare imposex and butyltin compounds (BTs) data, collected before and after the organotin ban in 2008, in order to assess temporal and spatial variation of the phenomenon, the decline of BT contamination, and the effects on Hexaplex trunculus population in the coastal area of the northern Adriatic Sea, close to the Venice Lagoon. Both in marine and in lagoon sites, the results obtained in 2013-2015 showed a significant decline in the incidence of imposex in respect to those from the 2002 survey. In 2002, lagoon samples exhibited Relative Penis Size Index (RPSI) higher than marine samples, whereas no differences were detected in the recent survey, when all RPSI values were below 0.6%. Vas Deference Sequence Index (VDSI) mean values were over 4 before the ban introduction and below this value after that, indicating more critical conditions for gastropod population in 2002 rather than in 2013-15. Percentage of sterile females was up to 69% in 2002, whilst in the more recent survey no sterile female was found. Range of BT concentrations in gastropods decreased from 252 to 579 to 16-31ng∑BT/g d.w. BT body burdens varied according to a gender dependant pattern, with higher concentrations observed in females than in males. A first attempt to propose a classification based on BT impact on H. trunculus, according to the Water Framework Directive, revealed that most sites were in Bad ecological status before the ban and attained a Poor/Moderate status after that.

Imposex in Nassarius nitidus (Jeffreys, 1867) as a possible investigative tool to monitor butyltin contamination according to the Water Framework Directive: A case study in the Venice Lagoon (Italy).

Butyltin (TBT, DBT, and MBT) effects on molluscs, especially endocrine disruption in bivalves and gastropods, have been widely investigated. Imposex, the superimposition of male characters onto female gonochoristic Caenogastropods, is the most studied biological effect of TBT. TBT compounds are among the priority hazardous substances within Directives 2000/60/EC (WFD) and 2008/105/EC. The Environmental Quality Standards (EQSs) set by the WFD for TBT are quite difficult to quantify by means of chemical analysis, without the use of expensive and high performance methods. Assuming that EQSs set for TBT were derived from evidence of imposex development at very low concentrations, this specific biomarker could be used as an indirect measure of assessing levels of bioavailable BTs. Therefore, this study aims to validate the use of imposex development as an investigative tool to monitor the bioavailable fraction of BTs within the WFD, by comparing imposex levels and BT concentrations in Nassarius nitidus from the Venice Lagoon. BT concentrations and imposex levels in N. nitidus, collected in 2013, had decreased when compared to previous studies in the same area. Both VDSI and RPLI correlated positively with BT body burden in females, confirming that imposex is a valid tool to monitor bioavailable BTs. However, TBT is still a matter of concern in the Venice Lagoon, as TBT concentrations were still higher than its degradation products suggesting recent fresh TBT inputs in the studied area. To propose imposex levels as an indicator of the impact of BTs within the WFD, classification class boundaries and Ecological Quality Ratios were introduced. As a preliminary attempt, imposex levels were also compared to the OSPAR Commission EcoQOs which linked imposex levels in Nassarius reticulatus with TBT concentrations in water. Based on this comparison the degree of imposex development in the Venice Lagoon suggested that TBT concentrations in water should be over the EQS-AA concentration and, at one site, also over the EQS-MAC. From all the results obtained in this work, it appears that imposex evaluation in N. reticulatus could give information about the ecological status regarding BT compounds under the WFD and also be used to monitor their effects and support chemical analyses until more sensitive methods become available.

PAH (Polycyclic Aromatic Hydrocarbon) bioaccumulation and PAHs/shell weight index in Ruditapes philippinarum (Adams & Reeve, 1850) from the Vallona lagoon (northern Adriatic Sea, NE Italy).

The Vallona lagoon is a transitional area located in the Po River delta (NE, ITALY) traditionally exploited for Manila clam (Ruditapes philippinarum) farming. During 2007-2008, a pipeline was buried in the middle of the lagoon to connect an off-shore structure to facilities on land. PAH levels were monitored in Manila clams and sediments before, during and after the pipeline construction to assess the impact of the activities through the pattern of distribution of the PAH compounds. PAH bioaccumulation in clams displayed seasonal fluctuations with higher levels in autumnal and wintry surveys than in spring-summer. Principal component analysis applied to PAHs in clams highlighted a petrogenic input during ante operam period and a pyrolytic origin during the burying activities. On the contrary, sediment PAH concentrations resulted quite similar both among sites and periods. Biota-Sediment-Accumulation-Factor values also confirmed that sediments were not the major source of PAH pollution for clams in this study. The welfare of clams was examined through two physiological indices (condition index and survival in air) to check the effects of the activities on a commercial resource. Both physiological indices exhibited seasonal variations connected to natural endogenous and exogenous factors; however survival in air was the most sensitive index in highlighting the effects of the pipeline burying activities. Finally, to ensure that PAH bioavailability assessment was not affected by seasonal variation of soft tissues of molluscs, PAHs/shell weight index was applied. Higher levels of this index were observed before and during the burying activities, whilst, after that, values significantly lowered. Moreover, the normalization enabled us to highlight the PAH uptake from clams in some particular periods and to compare different populations in a long-term biomonitoring program with data obtained from different periods of the year.

Platform of integrated tools to support environmental studies and management of dredging activities.

Dredging activities can cause environmental impacts due to, among other, the increase of the Suspended Solid Concentration (SSC) and their subsequent dispersion and deposition (DEP) far from the dredging point. The dynamics of the resulting dredging plume can strongly differ in spatial and temporal evolution. This evolution, for both conventional mechanical and hydraulic dredges, depends on the different mechanisms of sediment release in water column and the site-specific environmental conditions. Several numerical models are currently in use to simulate the dredging plume dynamics. Model results can be analysed to study dispersion and advection processes at different depths and distances from the dredging source. Usually, scenarios with frequent and extreme meteomarine conditions are chosen and extreme values of parameters (i.e. maximum intensity or total duration) are evaluated for environmental assessment. This paper presents a flexible, consistent and integrated methodological approach. Statistical parameters and indexes are derived from the analysis of SSC and DEP simulated time-series to numerically estimate their spatial (vertical and horizontal) and seasonal variability, thereby allowing a comparison of the effects of hydraulic and mechanical dredges. Events that exceed defined thresholds are described in term of magnitude, duration and frequency. A new integrated index combining these parameters, SSCnum, is proposed for environmental assessment. Maps representing the proposed parameters allow direct comparison of effects due to different (mechanical and hydraulic) dredges at progressive distances from the dredging zone. Results can contribute towards identification and assessment of the potential environmental effects of a proposed dredging project. A suitable evaluation of alternative technical choices, appropriate mitigation, management and monitoring measure is allowed in this framework. Environmental Risk Assessment and Decision Support Systems (DSS) may take advantage of the proposed tool. The approach is applied to a hypothetical dredging project in the Augusta Harbour (Eastern coast of Sicily Island-Italy).

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.

A fast and effective routine method based on HS-SPME-GC-MS/MS for the analysis of organotin compounds in biota samples.

This work validated an automated, fast, and low solvent- consuming methodology suited for routine analysis of tributyltin (TBT) and degradation products (dibutyltin, DBT; monobutyltin, MBT) in biota samples. The method was based on the headspace solid-phase microextraction methodology (HS-SPME), coupled with gas chromatographic separation and tandem mass-spectrometry (GC-MS/MS). The effectiveness of the matrix-matched signal ratio external calibration was tested for quantification purposes. The exclusion of matrix influences in the calibration curves proved the suitability of this versatile quantification method. The method detection limits obtained were of 3 ng Sn g(-1) dw for all the analytes. The analysis of references materials showed satisfying accuracy under optimum calibration conditions (% recovery between 87-111%; |Z-scores|<2). The repeatability RSD% and intra-laboratory reproducibility RSD% were lower than 9.6% and 12.6%, respectively. The work proved the remarkable analytical performances of the method and its high potential for routine application in monitoring organotin compounds (OTC).

Efficacy and maintenance strategies of two-compound formulation calcipotriol and betamethasone dipropionate gel (Xamiol® gel) in the treatment of scalp psoriasis: results from a study in 885 patients.

BACKGROUND: Previous studies showed the efficacy of a formulation containing calcipotriol and betamethasone dipropionate for the treatment of psoriasis. OBJECTIVE: To investigate maintenance strategies of a formulation containing calcipotriol (50 µg/g) and betamethasone dipropionate (0.5 mg/g) for the treatment of scalp psoriasis. MATERIALS AND METHODS: Nine-hundred and four patients were screened and randomised on a 1:1 basis in two groups: maintenance of two applications per week (group A) versus on-demand therapy (group B). Clinical evaluation was performed at weeks 0, 2, 4, 8 and 12. RESULTS: Eight-hundred and eighty-five patients were randomised: 441 in group A and 444 in group B. From week 2, both groups showed a significant clinical improvement compared with baseline; at weeks 8 and 12, group A demonstrated a higher clinical response compared with group B (p < 0.05). This difference was statistically significant (OR 0.47, 95% CI 0.37, 0.60). CONCLUSIONS: The maintenance of twice-weekly application versus on-demand treatment of calcipotriol/betamethasone dipropionate gel is more effective and is associated with a lower rate of relapse.

Emerging applications of nanomedicine in dermatology.

BACKGROUND: Nanotechnology is a new branch of engineering consisting of the usage of nanoscale particles (100 nm and smaller). Nanomedicine is the application of nanoscale technologies for diagnostic and therapeutic purposes in medicine. Nanodermatology, nanotechnology applied to dermatology, represents one of the most advanced field for which an increasing interest, both economic and scientific, is rising. The skin is the first point of contact for a whole host of nanomaterials, ranging from topical preparations, articles of clothing and household products, to sporting goods and industrial manufactured goods. Applications of nanomedicine in dermatology include new direction in medical diagnosis, monitoring and treatment. Gold nanoparticle, quantum dots and magnetic nanoparticles are used in non-invasive nanoimaging of high-resolution dermoscopy, microscopy, nanopunch, and spectroscopy, offering advanced diagnostic and therapeutic modalities. Nanotherapeutics has been considered in immunotherapy, genetherapy, and drug therapy. In drug therapy, because of size reduction or encapsulation of drug particles, the therapeutic potential of water insoluble and unstable drugs improve, and also facilitate the delivery of small molecules across blood, skin, nails, and pilosebaceous unit. AIMS: To review therapeutic applications and benefits of nanomedicine in esthetic dermatology, treatment of malignancies, and inflammatory skin diseases.

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.

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.

Bioremediation of petroleum hydrocarbons in anoxic marine sediments: consequences on the speciation of heavy metals.

We investigated the effects of biostimulation and bioagumentation strategies applied to harbor sediments displaying reducing conditions and high concentrations of petroleum hydrocarbons and heavy metals. We compared the microbial efficiency of hydrocarbon removal from sediments maintained for 60 days in anoxic conditions and inoculated with acetate, sulfate-reducing bacterial strains and acetate and sulfate-reducing bacteria. All treatments determined a significant increase in the microbial growth and significant decreases of hydrocarbon contents and of redox potential values. The addition of sulfate-reducing bacterial strains to the sediment was the most efficient treatment for the hydrocarbon removal. In all experiments, significant changes of the heavy metals' phase repartition were observed. The results reported here suggest that the biodegradation of petroleum hydrocarbons in anoxic marine sediments may be enhanced by stimulating microbial anaerobic metabolism, but care should be applied to monitor the potential changes in the mobility and bioavailability of heavy metals induced by bio-treatments.

Seasonal, spatial and inter-annual variations of trace metals in mussels from the Adriatic sea: a regional gradient for arsenic and implications for monitoring the impact of off-shore activities.

Mussels are widely used as bioindicator organisms for monitoring chemical pollutants including trace metals. These elements are natural constituents in the marine environment and their basal concentrations in the organisms can be influenced by several environmental and biological factors. The aim of this work was to extend our knowledge on the natural variability of trace metals in mussels tissues, focusing on seasonal and inter-annual fluctuations in a coastal reference site of the Adriatic coast (Portonovo); a total of 39 samplings were performed during 5 years, providing an extended data-set for tissue levels of As, Ba, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, V and Zn. Concentrations of trace metals in mussels tissues revealed marked seasonal fluctuations with significant differences between various sampling years. Such fluctuations appeared mostly related to phytoplanctonic blooms and especially to reproductive cycle which exhibited a certain inter-annual shift of the gametogenesis period. Lower concentrations were measured in summer months for the majority of elements while a different seasonal cycle was observed for arsenic, not correlated with gonadic development, neither with other elements. Chemical speciation of arsenic was characterized to distinguish compounds of natural origin from those potentially reflecting an anthropogenic impact. Arsenobetaine and arsenocholine were always the predominant forms (up to 85% of total arsenic), while a significant increase of dimethylarsine and trimethylarsine oxide in spring (24% of total arsenic) might reflect the effect of phytoplanctonic bloom on both geochemistry and trophic transfer of this element. A significant inter-annual variability was observed for both the seasonal cycle and the range of values measured for all the elements, with particularly marked differences for arsenic, ranging from less than 10 to more than 40 microg/g in summer periods of different years. Data obtained on reference mussels were used to assess the impact of 41 off-shore platforms distributed along 5 nautical districts in the Northern and Central Adriatic Sea. Organisms sampled on these structures from 2001 to 2005 exhibited a certain enrichment of cadmium and zinc, probably associated to the use of anodic electrodes. Marked annual and geographical variations were measured for concentrations of arsenic in mussels of different platforms. However, the comparison with results of Portonovo, allowed to exclude the anthropogenic impact of exploitation activities and revealed a natural regional gradient of arsenic levels in mussels tissues associated to the changing influence of the Po river runoff on seawater salinity. In particular the higher concentrations measured in organisms sampled from platforms in the Central compared to Northern Adriatic confirmed a significant relationship between salinity and arsenic bioaccumulation, consistent with a role of arsenobetaine as an acquired osmolyte for mussels. The overall results confirmed the importance of natural variability when assessing the potential impact of anthropogenic activities.

Seasonal variations of exposure biomarkers, oxidative stress responses and cell damage in the clams, Tapes philippinarum, and mussels, Mytilus galloprovincialis, from Adriatic sea.

This work investigated the natural variability of several biomarkers in Tapes philippinarum and Mytilus galloprovincialis, sampled from Northern Adriatic where these organisms are important sentinel species for future environmental impact assessment. Levels of metallothioneins, peroxisomal enzymes and acetylcholinesterase, showed a significant seasonality and marked differences between clams and mussels. Among antioxidant enzymes, catalase and GST decreased during the warmer period, the latter enzyme activity resulting particularly high in clams. The total oxyradical scavenging capacity toward peroxyl radicals decreased in mussels from winter to summer, indicating a prooxidant challenge due to higher seawater temperature and intensity of light irradiance. Lysosomal membrane stability did not exhibit significant seasonal variations, while some variations were observed for DNA damages. Overall results indicated a significant influence of seasonal variability on several biomarkers and species-specific differences which should be considered to discriminate the appearance of anthropogenic disturbance.

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.

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.