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Ethylene/1-octene statistical multiblock copolymers (OMBCs) consisting of the alternation of crystalline, hard blocks and amorphous, soft blocks, with ≈0.5 and 20 mol % of 1-octene units, respectively, are subjected to thermal fractionation resorting to successive self-nucleation and annealing (SSA). The study is extended to random copolymers (RCs) of high (44 kDa) and low (3.4 kDa) number average molecular mass Mn, mimicking in 1-octene content the crystalline hard blocks and to the OMBC fractions extracted in boiling n-hexane and cyclohexane through a suitable solution fractionation protocol. For all the samples, the melting endotherms are well resolved in a multiplicity of peaks corresponding to the melting of crystals of different thicknesses generated in the SSA protocol that reflect the distribution of the methylene sequence length (MSL) in between consecutive interruptions along the chains. It is shown that, regardless of molecular mass, the MSL distributions of the RC samples are shifted toward greater values than those of the OMBC samples, and that also the shapes of the distributions are different. Since the MSL distribution depends on the frequency and distribution of the defects along the chains, and the defects act as interruption points, the higher fraction of long crystallizable sequences in the RC samples suggests that whereas for the RC samples the interruptions are merely represented by the 1-octene units that are rejected outside the crystals, for the OMBCs, the interruption of the regular methylene sequences belonging to the crystalline hard blocks due to the amorphous soft blocks linked to them should also play a role. Indeed, due to the partial miscibility of the hard and soft blocks, the hard blocks of major length tend to crystallize in a confined environment. This prevents the formation of thicker crystals and induces decrease of the MSL values as well as changes in the shape of the MSL distributions (topological confinement). On the other hand, the hard blocks of shorter length tend to crystallize, crossing the hard block rich regions and causing melting point depression and consequent shift of the MSLs toward lower values with respect to RCs (diluent effect). It is shown that differences in the MSL distribution of OMBCs are the result of the interplay between topological confinement and diluent effect, which in turn reflects differences in the OMBC chain microstructure, that is, differences in the distribution of block length at the inter- and intra-chain level.

The present study was aimed at identifying geospatial patterns of pollutants including concentrations and toxicity as complex environmental mixtures, in topsoil samples close to petrochemical facilities in the heavily industrialized area of Augusta and Priolo in south-eastern Sicily (Italy). Elemental analysis of soil was conducted by ICP-MS for 23 metals and 16 rare earth elements (REEs). Organic analyses were primarily focused on polycyclic aromatic hydrocarbons (PAHs) (16 parent homologs) and total aliphatic hydrocarbons (C10 – C40). Topsoil samples were tested for toxicity in multiple bioassay models including: 1) developmental defects and cytogenetic anomalies in sea urchin Sphaerechinus granularis early life stages ; 2) growth inhibition of diatom Phaeodactylum tricornutum ; 3) mortality in nematode Caenorhabditis elegans ; and 4) induction of mitotic abnormalities in onion Allium cepa. Samples collected at sites closest to defined petrochemical facilities were highest in select pollutants and correlated with biological effects in different toxicity endpoints. A noteworthy finding was the increased level of total REEs in sites closest to petrochemical facilities, suggesting their contributions to identifying petrochemical sources of pollutants to the environment. The combined data obtained in the different bioassays allowed exploration of geospatial patterns of effect in biota as a function of contaminant levels. In conclusion, this study provides consistent data of soil toxicity, metal and REE contamination at Augusta- Priolo sampling sites, and may provide an appropriate baseline for epidemiological studies on high incidences of congenital birth defects in the area and identification of at-risk localities.

Macro and trace elements are important regulators of biological processes, including those ones linked to reproduction. Among them, Ca, Cu, Fe, K, Mg, Mn, Na, Se, and Zn ensure normal spermatic functions. Hence, the aim of this study was to evaluate the concentrations of 26 macro and trace elements (Al, As, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Li, Mg, Mn, Na, Ni, Pb, Rb, Sb, Se, Sn, Sr, U, V, and Zn) in blood serum and also in semen of healthy young men, homogeneous for age, anthropometric characteristics, and lifestyle, living in three highly polluted areas in Italy. Furthermore, a comparison among three geographical areas was performed to highlight any difference in the investigated parameters and, overall, to speculate any correlations between chemical elements and semen quality. Statistically significant differences (p < 0.05) among the three areas were found for each investigated element, in both semen and serum samples, where inter-area differences were more evident in semen than in blood serum, suggesting human semen as an early environmental marker. Considering the homogeneity of three cohorts, these differences could be due more to environmental conditions in the recruiting areas, suggesting that variations in those involved in reproductive-associated pathways can have an impact on male fertility. Nevertheless, more research is needed to evaluate threshold values for sperm dysfunction and male infertility. Actually, the role of different dietary intake and environmental exposure underlying the observed differences in the recruiting areas is under further investigation for the same cohort.

The study deals with the analyses of springs and wells at the base of Montepugliano Hill that represents the SE edge of the wide carbonate Matese massif (Campania, southern Italy). At the base of the hill, from west to east and for almost one kilometre, cold springs HCO3-Ca type (Grassano springs, ~ 4.5 m3/s; TDS: about 0.45 g/L) pass to hypothermal, HCO3-Ca type, sulphurous and CO2-rich springs (~ 1 m3/s with TDS > 1 g/L). Some of the latter are widely used inTelese SpaandCentro Relax Spa.Chemical and isotopic analyses carried out for this study support the hypothesis that all these waters (mineral and non-mineral) have the same catchment area, which is located in the Matese massif. As regards the sulphurous springs, they receive both meteoric waters infiltration and uprising of deeper waters rich in endogenous CO2and H2S gases through important faults systems. Far from these faults, the chemistry of groundwater is scarcely (or not at all) affected by these deep fluid enrichment processes. This scheme is very significant; in fact, when very important groundwater resources are present, it is possible to use both mineral waters in Spa and, in areas far from the faults, those not yet mineralized. Finally, at Montepugliano Hill, in the final stage of the flow path, groundwater is also affected by change in the microbiome: this could provide a basis for comparison between various mineral waters.

Climate change has strongly increased the fire frequency in Mediterranean forests causing changes in soil bacterial, fungal and microarthropod communities. Fire impacts on soil properties depend on vegetation covers. In this framework, the aim of this research was to evaluate the effects of fire on bacterial, fungal communities and microarthropod community in soils under trees and shrubs in a Mediterranean area. Surface soil cores were sampled in unburnt and burnt (three years since fire occurrence) patches in the Vesuvius National Park trees (Quercus ilex L. and Pinus nigra L.) and shrubs (Ginesta sp., Myrtus communis L., Laurus nobilis L.). Samples were analyzed for abiotic (pH, water content and concentrations of C, N, Corg, P, NO2 NH4+ and Pavail) and biotic (bacterial and fungal biomasses, and density, taxa richness, diversity, evenness and QBS-ar of microarthropods) properties. Results showed that, three years since fire, the abiotic properties were recovered in shrub stands but not yet in tree stands. Fire stimulated the development of bacteria only in shrub stands; no effects were observed for the fungal community in both shrub and tree stands; the amount and the taxa richness of microarthropods recovered to the values of the pre-fire conditions in both the stands. In conclusion, in the investigated area, fire differently impacted the vegetation covers, making soils under trees more similar to shrubs with the consequence to reduce the differences between the vegetation covers

Aluminium, despite being extremely widespread in the world, is a non-essential metal to human metabolism. This metal is known to have toxic effects on a variety of organs including the brain and is considered an etiological factor in neurodegenerative diseases. However, the molecular mechanisms by which aluminium exerts neurotoxic effects are not yet completely understood. Zebrafish is an animal model also used to study neurodegenerative diseases since the overall anatomical organization of the central nervous system is relatively conserved and similar to mammals. Adult zebrafish were exposed to 11 mg/L of Al for 10, 15, and 20 days and the neurotoxic effects of aluminium were analysed by histological, biochemical, and molecular evaluations. Histological stainings allowed to evaluation of the morphology of the brain parenchyma, the alteration of myelin and the activation of neurodegenerative processes. The expression of the Glial Fibrillary Acidic Protein, a marker of glial cells, was evaluated to observe the quantitative alteration of this important protein for the nervous system. In addition, the poly(ADP-ribose) polymerase activity was measured to verify a possible oxidative DNA damage caused by exposure to this metal. Finally, the evaluation of the markers involved in Parkinsonism was assessed by Real-Time PCR to better understand the role of aluminium in the regulation of genes related to Parkinson's neurodegenerative disease. Data showed that aluminium significantly affected the histology of cerebral tissue especially in the first periods of exposure, 10 and 15 days. This trend was also followed by the expression of GFAP. At longer exposure times, there was an improvement/stabilization of the overall neurological conditions and decrease in PARP activity. In addition, aluminium is involved in the deregulation of the expression of genes closely related to Parkinsonism. Overall, the data confirm the neurotoxicity induced by aluminium and shed a light on its involvement in neurodegenerative processes.

The aim of this study was to compare the relative nutritional benefit of edible Malaysian fishes from the coast of Terengganu in Malaysia, as well as to perform a taxonomical characterization and metal assessment. Discrimination between species was carried out by a morphological and molecular approach by evaluating the total concentrations of metals by ICP-MS analyses and the fatty acids (FA) composition using the GC–MS approach on the fish fillet tissues. The taxonomical studies detected fishes of 11 families and 13 species. The heavy metal assessment showed that all detected elements did not exceed the regulatory limit stated by Malaysian Food Regulations. The proportion of saturated fatty acids (SFA) ranged from 33 to 58.34%, followed by the polyunsaturated fatty acids (PUFA) values from 24 to 51.8%, and the lowest proportion was of monounsaturated fatty acids (MUFA), ranging from 12.7 to 35.9%. The ω-3/ω-6 PUFA and PUFA/SFA ratios were determined in the range 1.1 to 7.4 and 0.35 to 1.6, respectively. The C20:5 ω-3 and C22:6 ω-3 acids were detected at levels comparable to those found in the corresponding species from similar tropical marine ecosystems. The high FA values can be useful biochemical tools for comparing the relative nutritional benefits of these biodiverse and non-toxic edible Malaysian fishes.

Mediterranean regions are the most impacted by fire in Europe. The effects of fire on soil greatly vary according to several factors such as vegetation cover type, but they are scarcely studied. Therefore, this research aimed at evaluating the combined impacts of fire and vegetation on single soil characteristics and on the overall soil quality and functionality through two soil quality indices, simple additive (SQI) and a weighted function (SQIFUNCT). In order to reach the aims, burnt and unburnt soils were collected under different vegetation cover types (herbs and shrubs, black locust, pine and holm oak) within the Vesuvius National Park. The soils were analyzed for the main abiotic (water and organic matter content, total C, N, Ca, K, Cu and Pb concentrations, C/N ratio) and biotic (microbial and fungal biomasses, basal respiration, β-glucosidase activity) characteristics. On the basis of the investigated soil characteristics, several soil functions (water retention, nutrient supply, contamination content, microorganism habitat and activities), and the soil quality indices were calculated. The results showed that the impact of fire on soil quality and functionality was mediated by the vegetation cover type. In fact, fire occurrence led to a decrease in water and C/N ratio under herbs, a decrease in C concentration under holm oak and a decrease in Cu and Pb concentrations under pine. Although the soil characteristics showed significant changes according to vegetation cover types and fire occurrence, both the additive and weighted function soil quality indices did not significantly vary according to both fire occurrence and the vegetation cover type. Among the different vegetation cover types, pine was the most impacted one.

Mercury (Hg) is an environmental pollutant that impacts human and ecosystem health. In our previous works, we reported alterations in the properties of Mytilus galloprovincialis protamine-like (PL) proteins after 24 h of exposure to subtoxic doses of toxic metals such as copper and cadmium. The present work aims to assess the effects of 24 h of exposure to 1, 10, and 100 pM HgCl2 on spermatozoa and PL proteins of Mytilus galloprovincialis. Inductively coupled plasma–mass spectrometry indicated accumulation of this metal in the gonads of exposed mussels. Further, RT-qPCR analyses showed altered expression levels of spermatozoa mt10 and hsp70 genes. In Mytilus galloprovincialis, PL proteins represent the major basic component of sperm chromatin. These proteins, following exposure of mussels to HgCl2, appeared, by SDS-PAGE, partly as aggregates and showed a decreased DNA-binding capacity that rendered them unable to prevent DNA damage, in the presence of CuCl2 and H2O2. These results demonstrate that even these doses of HgCl2 exposure could affect the properties of PL proteins and result in adverse effects on the reproductive system of this organism. These analyses could be useful in developing rapid and efficient chromatin-based genotoxicity assays for pollution biomonitoring programs.

Mercury (Hg) is a highly toxic and widespread pollutant. We previously reported that the exposure of Mytilus galloprovincialis for 24 h to doses of HgCl2 similar to those found in seawater (range 1–100 pM) produced alterations in the properties of protamine-like (PL) proteins that rendered them unable to bind and protect DNA from oxidative damage. In the present work, to deepen our studies, we analyzed PL proteins by turbidimetry and fluorescence spectroscopy and performed salt-induced release analyses of these proteins from sperm nuclei after the exposure of mussels to HgCl2 at the same doses. Turbidity assays indicated that mercury, at these doses, induced PL protein aggregates, whereas fluorescence spectroscopy measurements showed mercury-induced conformational changes. Indeed, the mobility of the PLII band changed in sodium dodecyl sulphate-polyacrylamide gel electrophoresis, particularly after exposure to 10-pM HgCl2, confirming the mercury-induced structural rearrangement. Finally, exposure to HgCl2 at all doses produced alterations in PL-DNA binding, detectable by DNA absorption spectra after the PL protein addition and by a decreased release of PLII and PLIII from the sperm nuclei. In conclusion, in this paper, we reported Hg-induced PL protein alterations that could adversely affect mussel reproductive activity, providing an insight into the molecular mechanism of Hg-related infertility.

Mercury (Hg) is an environmental pollutant that impacts human and ecosystem health. In our previous works, we reported alterations in the properties of Mytilus galloprovincialis protamine-like (PL) proteins after 24 h of exposure to subtoxic doses of toxic metals such as copper and cadmium. The present work aims to assess the effects of 24 h of exposure to 1, 10, and 100 pM HgCl2 on spermatozoa and PL proteins of Mytilus galloprovincialis. Inductively coupled plasma–mass spectrometry indicated accumulation of this metal in the gonads of exposed mussels. Further, RT-qPCR analyses showed altered expression levels of spermatozoa mt10 and hsp70 genes. In Mytilus galloprovincialis, PL proteins represent the major basic component of sperm chromatin. These proteins, following exposure of mussels to HgCl2, appeared, by SDS-PAGE, partly as aggregates and showed a decreased DNA-binding capacity that rendered them unable to prevent DNA damage, in the presence of CuCl2 and H2O2. These results demonstrate that even these doses of HgCl2 exposure could affect the properties of PL proteins and result in adverse effects on the reproductive system of this organism. These analyses could be useful in developing rapid and efficient chromatin-based genotoxicity assays for pollution biomonitoring programs.

In our previous work, we reported alterations in protamines/histones ratio, in DNA binding of these proteins and their involvement in DNA oxidative damage in 84% of the young men living in the Land of Fires. In the present work, we extended our findings, evaluating any alterations in spermatozoa of a family case, a father and son, living in this area, to also give a first look at the possibility of transgenerational inherited effects of environmental contaminants on the molecular alterations of sperm nuclear basic proteins (SNBP), DNA and semen parameters. In the father and son, we found a diverse excess of copper and chromium in the semen, different alterations in SNBP content and low DNA binding affinity of these proteins. In addition, DNA damage, in the presence of CuCl2 and H2O2, increased by adding both the father and son SNBP. Interestingly, son SNBP, unlike his father, showed an unstable DNA binding and were able to produce DNA damage even without external addition of CuCl2, in line with a lower seminal antioxidant activity than the father. The peculiarity of some characteristics of son semen could be a basis for possible future studies on transgenerational effects of pollutants on fertility.

DNA oxidative damage is one of the main concerns being implicated in severe cell alterations, promoting different types of human disorders and diseases. For their characteristics, male gametes are the most sensitive cells to the accumulation of damaged DNA. We have recently reported the relevance of arginine residues in the Cu(II)-induced DNA breakage of sperm H1 histones. In this work, we have extended our previous findings investigating the involvement of human sperm nuclear basic proteins on DNA oxidative damage in healthy males presenting copper and chromium excess in their semen. We found in 84% of those males an altered protamines/histones ratio and a different DNA binding mode even for those presenting a canonical protamines/histones ratio. Furthermore, all the sperm nuclear basic proteins from these samples that resulted were involved in DNA oxidative damage, supporting the idea that these proteins could promote the Fenton reaction in DNA proximity by increasing the availability of these metals near the binding surface of DNA. In conclusion, our study reveals a new and unexpected behavior of human sperm nuclear basic proteins in oxidative DNA damage, providing new insights for understanding the mechanisms related to processes in which oxidative DNA damage is implicated.

In this study, the performance of 63 existing pedotransfer functions (PTFs) is evaluated to estimate oven-dry soil bulk density (BD) by using a dataset of 3316 soil cores taken in the farmlands of Campania (southern Italy). As expected, the lack of direct calibration yields prediction accuracy from unsatisfactory to rather weak. Therefore, we advance the working hypothesis that the use of hierarchical soil mapping information can make the application of existing PTFs more reliable. We show that grouping data according to land-systems classes or soil groups considerably improves the prediction ability quantified through the root mean squared error (RMSE) and the coefficient of determination (R2). An independent data set of 105 soil cores taken from two hillslopes in the Upper Alento River Catchment in southern Campania was used to verify our assumption. The validation step shows that the knowledge of a soil-landscape map is an efficient tool for improving the prediction of BD. This approach will be employed in a subsequent study to develop site-specific PTFs for the study region.

In urban areas, particulate matter (PM) is the most abundant airborne pollutant. Plants have been reported to filter PM, as leaves may intercept and adsorb it. The aims of the research were: i) to evaluate if leaves of Quercus ilex L., an ornamental species proven to be a good monitor of air quality, of different ages (1 and 2 years old) differed for the main leaf traits; ii) to assess the efficiency of Q. ilex L. leaves of different ages to intercept particulate matter of two sizes (PM>10 and PM10); iii) to highlight the leaf traits that enhanced the accumulation of PM>10 and PM10 on leaf surface. The research was performed at four municipalities on the outskirts of Naples (Southern Italy). In April 2018, Q. ilex L. leaves of one and two years old were collected and then described for length, width, area, thickness, circularity, dry matter content and petiole length. The tested hypotheses were: older leaves, that should have high values of the investigated leaf traits, intercept and accumulate greater amounts of PM; leaves with greater circularity, width and length, and with lower dry matter content are expected to accumulate more PM. The findings highlighted that Q. ilex leaves of different ages did not statistically differ neither for the investigated leaf traits nor for the amounts of accumulated PM>10 and PM10; the greater amount of PM was observed in Q. ilex leaves with higher circularity and lower dry matter content; smaller width leaves seem to favour the accumulation of PM>10 and those with smaller length the accumulation of PM10.

Water kept in contact with cellulose has not been a “juicy” research topic until now. This is surprising because cellulose is a major component of the cell walls in green plants. It is also a common material used in many artificial systems, e.g., filters. In this work, we review some of our experimental results and show that iteratively bringing cellulose (cotton wool) in contact with pure water endows the water with some unforeseen properties. For example, the liquid left over after removing the cellulose is optically active, i.e., mirror symmetry breaking was triggered during temporary contact of bulk water with a natural polymer. (Here and in the following, by “mirror” symmetry we actually mean “chiral” symmetry). Moreover, this leftover liquid fluoresces after irradiation with ultraviolet light. These properties are neither attributable to impurities released by the inert polymer nor to organic- or bio-contaminants, as our state-of-the-art analytical techniques show. These techniques include gel electrophoresis, Matrix-Assisted Laser Desorption/Ionization Time of Flight (MALDI-TOF) and Gas Chromatography both coupled with Mass Spectrometry. Instead, the properties are attributable to stabilization of interfacial water adjacent to hydrophilic membranes. Our findings have implications for processes in water flowing adjacent to cellulose, in particular enantioselective processes. Such processes play critical roles in many bio-systems and technologies. Thus, our study indicates that water iteratively brought in contact with cellulose merits intensive research.

A hydrogeological and hydrogeochemical survey in the Cumae archaeological site (Phlegraean Fields, southern Italy) together with radon levels determination in groundwater have been carried out. The study was motivated by the fact that the site is often submerged by the outcrop of groundwater, threatening the integrity of ruins, and hence by the need to preserve such important archaeological park. The hydrostratigraphic and hydrogeological data revealed the presence of a multi-layered aquifer system, formed by a shallow unconfined and a deep semiconfined aquifer. The groundwater flow appeared to be strongly influenced by vertical and lateral lithological heterogeneity of volcanic-sedimentary deposits, as well as by groundwater pumping and drainage by surface micro-channel system. The dominant hydrochemical facies were Cl−-SO42 −-Na+-K+, HCO3−-Ca2 +-Mg2 + and HCO3− Na+-K+ types. These facies were affected by: i) dissolution and chemical weathering, ion exchange with volcanic-sedimentary deposits, ii) localized rise along faults and fractured zones of deep magmatic fluids highly mineralized, with outstanding levels of F−, 6.4 mg L− 1 in deep water and 3.3 mg L− 1 in shallow water, and 222Rn, 31,500 Bq m− 3 in deep water and 5400 Bq m− 3 in shallow water; iii) freshwater-saltwater interactions, induced by groundwater pumping.

The widespread use of rare earth elements (REEs) in a number of technological applications raises unanswered questions related to REE-associated adverse effects. We have previously reported on the multiple impact of some REEs on the early life stages of the sea urchin Paracentrotus lividus. The present investigation was to evaluate REE toxicity to early life stages in two unrelated sea urchin species, Sphaerechinus granularis and Arbacia lixula. The comparative toxicities were tested of seven REEs, namely yttrium, lanthanum, cerium, neodymium, samarium, europium and gadolinium as chloride salts at concentrations ranging from 10-7 to 10-4 M. The evaluated endpoints included developmental defects and cytogenetic anomalies in REE-exposed embryos/larvae, and decreased fertilization success and offspring damage following sperm exposure. The results showed different toxicity patterns for individual REEs that varied according to test species and to treatment protocol, thus showing toxicity scaling for the different REEs. Further, the observed effects were compared with those reported for P. lividus either following embryo or sperm exposures. S. granularis showed a significantly higher sensitivity both compared to A. lixula and to P. lividus. This study provides clear-cut evidence for distinct toxicity patterns among a series of REEs. The differences in species sensitivity at micromolar REE levels may warrant investigations on species susceptibility to impacts along polluted coasts.

Phlegraean Fields, hydrogeological model, hydrochemical facies, Flowpath 2017, National meeting on hydrogeology 2017

The determination of the chemical composition of different parts of wall paintings (pigments, mortars and binders) provides information about technology of preparation of an artefact. Herein, we present a multi-methodological characterisation of wall paintings from a Roman archaeological site in Cuma, focusing on differences between an indoor (domus) and outdoor fabrication (a temple, Tempio con Portico (TCP)). Both pigments, binders and mortars were studied via a combination of destructive/μ-destructive (mass spectrometry, ionic chromatography, ICP-based techniques) and non-destructive (Raman microscopy, small-angle neutron scattering (SANS) and X-ray diffraction) methodologies. Particularly, the systematic presence of dolomite only in mortars from TCP may suggest an intentional use of such limestone for the outdoor fabrication of public interest. Differences between TCP and domus are also related to the composition of the pigment binder. In particular, the detected binders (studied by LC-MS/MS and GC-MS) were proteinaceous in the case of domus (possibly egg and animal glue) and drying oils in the case of TCP. Ultimately, our multi-methodological study provides an overall picture of the material components of paintings from fabrications with different use, proposing a hypothesis on technological choices according to conservative and destination reasons.

A multidisciplinary survey was carried out on the quality of water and sediments of the estuary of the Sele river, an important tributary of the Tyrrhenian Sea, to assess anthropogenic pressures and natural variability. Nine sediment sites were monitored and analyzed for granulometry, morphoscopy, benthic foraminifera and ostracod assemblages, heavy metals, and polycyclic aromatic hydrocarbons. Surface water was assayed for ionic composition and phytoplankton biomass. Total organic carbon (TOC) and total nitrogen (TN) in sediments were higher in the inner part of the estuary (IE), up to 12.7 and 0.7% because of anthropic influence. In waters, N-NH4, N-NO3, and Ptot. were high, with loads of Ptot in IE exceeding ~fourfold the limit. Here, it was also observed that the highest primary production was Chl-a, 95.70 &micro, g/L, with cryptophytes, 37.6%, and diatoms, 33.8%, being the main phytoplanktonic groups. The hierarchical analysis split the estuary into two areas, with marked differences in anthropic pollution. Waters were classified as poor&ndash, bad level with respect to the content of nutrients. Sedimentological assay reveals littoral erosion and poor supply of river sandy sediments. The erosion environment is confirmed by the presence of meiobenthic recent marine forms intrusion inside the river. All these data reveal the fragility of the estuary and the need of urgent remediation actions.

Here we report the industrial pollution effects due to cadmium on the reproductive health of Mytilus galloprovincialis. Mussels were removed from the biofouling of a Conatex panel after one year exposition at a polluted site near a disposal metallurgical factory. A high cadmium bioaccumulation was observed in the testis of mussels housed at the polluted site, with respect to a control site, as determined by inductively coupled plasma-mass spectrometry, along with a 10 fold increase in metallothionein 20 kDa gene (mt20) expression levels determined by qPCR. Furthermore, mussels transferred into laboratory tanks from the reference site, and exposed to 1.5, 5 and 10 mu M CdCl2, revealed a 1.7, 3.2 and 4.5 fold expression increase in the testis mt20, respectively, and a positive correlation with cadmium bioaccumulation was found. To evaluate a potential detrimental risk of such alterations on spermatozoa, we carried out electrophoretic analyses on their protamine-like proteins. As determined by AU-PAGE, after 1.5 mu M CdCl2 exposure, protamine-like proteins also display major alterations with respect to those obtained after 5 and 10 mu M CdCl2 exposure. All protamine-like proteins isolated from the polluted biofouling were in an aggregated form and displayed the same reduced DNA binding affinity of the protamine-like proteins obtained after 1.5 mu M CdCl2 as demonstrated EMSA with sperm genomic DNA. Our results contribute to the studies concerning cadmium induced testis alterations and highlight protamine-like proteins' analysis as an emerging biotechnique for cadmium impact assessment on Mytilus galloprovincialis, for the sensitivity of the in vivo and in vitro changes of protamine-like proteins' state and their DNA binding affinity.

Determination of the chemical composition of different parts of the wall paintings (pigments, mortars and binders) allows extracting information about technology of preparation of the artefact. Herein we present a multimethodological characterization of wall paintings from a Roman Archeological sites from Cuma, focusing on differences between indoor (domus) and outdoor (Temple) fabrication. Both pigments, binders and mortars were studied via a combination of destructive/microdestructutive (mass spectrometry, ionic chromatography, ICP-based techniques) and non-destructive (Raman microscopy, X-ray diffraction and SANS) methodologies. Particularly, the systematic presence of dolomite only in temple mortars suggests an intentional use of such limestone for outdoor fabrication. Differences between temple and domus extends also to binder composition: proteinaceous binders in domus (possibly egg [3] and animal glue), whereas in TCP no protein was detected but some fat acids (probably from animal fat). Ultimately, the multimethodological study allowed an overall picture of the components and technology of the paintings from fabrications with different use, proposing distinct engineering choices for indoor and outdoor walls.

Determination of the chemical composition of different parts of the wall paintings (pigments, mortars and binders) allows extracting information about technology of preparation of the artefact. Herein we present a multimethodological characterization of wall paintings from a Roman Archeological sites from Cuma, focusing on differences between indoor (domus) and outdoor (Temple) fabrication. Both pigments, binders and mortars were studied via a combination of destructive/microdestructutive (mass spectrometry, ionic chromatography, ICP-based techniques) and non-destructive (Raman microscopy, X-ray diffraction and SANS) methodologies. Particularly, the systematic presence of dolomite only in temple mortars suggests an intentional use of such limestone for outdoor fabrication. Differences between temple and domus extends also to binder composition: proteinaceous binders in domus (possibly egg [3] and animal glue), whereas in TCP no protein was detected but some fat acids (probably from animal fat). Ultimately, the multimethodological study allowed an overall picture of the components and technology of the paintings from fabrications with different use, proposing distinct engineering choices for indoor and outdoor walls. References [1] Cartechini L., Pucci P., Sgamellotti A., Marino G., Birolo L., “Proteomic strategies for the identification of proteinaceous binders in paintings” Analytical & Bioanalytical Chemistry 395(7), 2009, 2269-2280. [2] Gelzo M., Grimaldi M., Vergara A., Severino V., Chambery A., Dello Russo A., Piccioli C., Corso G,. Arcari P. "Comparison of binder composition in Pompeian wall painting styles from Insula Occidentalis" Chemistry Central J. 8(65), 2014, 1-10. [3] Vinciguerra R, Galano E, Vallone F, Greco G, Vergara A, Bonaduce I, Marino G, Pucci P, Amoresano A, Birolo L, “Deglycosylation Step to Improve the Identification of Egg Proteins in Art Samples” Analytical Chemistry 87 (20), 2015, 10178-10182. Acknowledgements This work was financially supported by Distretto ad Alta Tecnologia dei Beni Culturali (DATABENC scarl), progetto SNECS. “Soprintendenza Speciale per i Beni Archeologici di Napoli e Pompei” – Ufficio Archeologico di Cuma - Dr Paolo Caputo is also acknowledged.