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Studies on the molecular mechanisms of heavy metal toxicity in invertebrate reproduction are limited. Given that PARP-catalysed ADP-ribosylation is also involved in counteracting heavy metal toxicity and maintaining genomic integrity, and that PARylation is implicated in chromatin remodelling but its role in sperm chromatin remains to be elucidated, we investigated the effects of chromium(VI) at 1, 10 and 100 nM on the reproductive health of Mytilus galloprovincialis. The damage to the gonads was assessed by morphological analyses and the damage indices PARP and ɣH2A.X were measured. Changes in the binding of protamine-like (PL) to DNA and the possibility of poly(ADP-ribosyl)ation of PL proteins were also investigated. Gonadal chromium accumulation and morphological damage were found, especially when the mussels were exposed to the highest dose of chromium(VI). In addition, the maximum expression of gonadal ɣH2A.X and PARP were obtained at 100 and 10 nM Cr(VI), respectively. Interestingly, for the first time in all exposed conditions, poly(ADP)-ribosylation was detected on PL-II, which, together with PL-III and PL-IV, are the major nuclear basic proteins of Mytilus galloprovincialis sperm chromatin. Since PL-II is involved in the final high level of sperm chromatin compaction, this post-translational modification altered the binding of the PL protein to DNA, favouring the action of micrococcal nuclease on sperm chromatin. This study provides new insights into the effects of chromium(VI) on Mytilus galloprovincialis reproductive system and proposes a molecular mechanism hypothesis describing the toxic effects of this metal on PL-DNA binding, sperm chromatin and gonads., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

The essential utilization of rare earth elements (REEs) for the production of several electronic devices is making the demand for them being increased all the time. This extensive use of these elements has also increased concern about human and environmental health. Previous studies have shown that REE levels are higher in environmental samples near mining sites, and they are highly possible to be transferred to biota. In this study, REE levels were determined in environmental samples collected from three abandoned mining sites of bauxite (Gargano, Otranto, and Spinazzola) in the region of Puglia, Southern Italy. The samples were digested and analyzed by two different techniques, Total X-Ray Fluorescence (TXRF) and Inductively Coupled Plasma - Mass Spectroscopy (ICP-MS) to investigate which technique is the most suitable for analysis of the REE content in samples from abandoned mining sites of bauxite. Only 6 REEs could be detected by TXRF, while all REEs were detected in all the samples by ICP-MS. Spinazzola is the richest site and Ce the most abundant REE in all three regions. REE levels are correlated between the soil and biota samples in many cases, although the calculation of the bioconcentration factor showed that REEs are not bioaccumulative. ICP-MS seems to be a more suitable technique for analysis of the whole REE content in environmental samples from abandoned mining sites of bauxite., Competing Interests: Declaration of competing interest The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

This study investigates the ecotoxicological effects of BDE-209, a persistent organic pollutant (POP) prevalent in Kuwait's coastal-industrial areas, on benthic foraminiferal communities. We conducted a mesocosm experiment in which we exposed benthic foraminiferal communities sampled from the coastal-industrial areas of Kuwait to a gradient of BDE-209 concentrations (0.01 to 20 mg/kg). The impact of exposure was assessed using live-staining and metabarcoding techniques. Despite the significantly different taxonomic compositions detected by the two techniques, our results show that BDE-209 significantly affects foraminiferal communities, with moderately high concentrations leading to reduced α-diversity and considerable taxonomic shifts in both molecular and morphological assemblages. At concentrations of 10 and 20 mg/kg, no living foraminifera were detected after 8 weeks, suggesting a threshold for their survival under BDE-209 exposure. The parallel responses of molecular and morphological communities confirm the reliability of both assessment methods. This study is the first to investigate the reaction of eukaryotic communities, specifically foraminifera, to POPs such as BDE-209, generating valuable insights that have the potential to enhance field studies and aid the refinement of sediment quality guidelines., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The levels of polycyclic aromatic hydrocarbons, PAHs, were determined in the liver and salt gland of 19 loggerhead turtles (Caretta caretta Linnaeus, Cheloniidae) stranded along the coasts of the south Tyrrhenian Sea, Italy, from 2019 to 2021. The 16 EPA's priority PAHs were determined by gas chromatography coupled with mass spectrometry (GC-MS). The average values of ΣPAHs in liver, 139 ± 55.0, were exceptionally high and up to one hundred times those of literature and appeared even more worrying in salt gland, 320 ± 97.6 ng/g, w.w. Naphthalene was the predominant contributor to PAHs richness and accounted for 90.0% and 93.7% of ΣPAHs in the two matrices, highlighting the petrogenic source of exposure. An overall higher bioaccumulation of NAP, more than two-fold, was detected in salt gland and especially in female and adults. Data of PAHs richness highlighted a potential risk of neoplastic disease development and that anthropogenic activities may seriously impair healthy state conditions of C. caretta. populations in south Tyrrhenian Sea., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

We explored relationships between particulate matter (PM) and polycyclic aromatic hydrocarbon (PAHs) leaf concentrations, uptake rates and leaf surface functional traits in four Mediterranean evergreen trees (Chamaerops humilis, Citrus × aurantium, Magnolia grandiflora, and Quercus ilex) during a dry month. Pollutant leaf concentration at different dates and uptake rate were correlated. We quantified PM by gravimetric analysis, PAHs were extracted from intact and dewaxed leaves and analyzed by GC-MS, and cuticle thickness, number and surface of stomata (N s and S S ) and trichomes (N t and S t ) were determined by optical microscopy. Infrared spectroscopy was used to investigate the leaves surfaces composition and assess esterification index (E). Studied species were characterized by unique combinations of functional traits and pollutant uptake capacities. PM 10 uptake scaled positively with S S , S t and upper cuticle thickness (T c,u ) across species. PM 2.5 uptake scaled positively with T c,u , and thicker cuticles were also associated with greater shares of uptake of hydrophobic PM fractions. Uptakes of different fractions of PAH were generally weakly related to different leaf functional traits, except for some correlations with E and S S . We conclude that both plant surface morphological and chemical leaf traits influence PM and PAH retention, unveiling their potential role in air phytoremediation., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Significant release of rare earth elements (REEs) into the environment is mainly due to active or abandoned mining sites, but their presence is globally increasing due to their use in several industrial sectors. The effects on primary producers as Raphidocelis subcapitata are still limited. This research focused on La and Ce as the two most widespread REEs that can be currently found up to hundreds of μg/L in water and wastewater. Microalgae were exposed to La and Ce for 3 days (pH = 7.8) (short-term exposure) to derive the effective concentrations inhibiting the growth on 10% (EC10) of the exposed population. EC10 values (0.5 mg/L of La and 0.4 mg/L of Ce) were used for the 28 days long-term exposure (renewal test) to observe after 7, 14, 21, and 28 days on a multi-endpoint basis microalgae growth inhibition (GI), biomarkers of stress (reactive oxygen species (ROS), superoxide dismutase (SOD), and catalase (CAT)), and bioconcentration. Results evidenced that La and Ce EC10 increased GI (day 28) up to 38% and 28%, respectively. ROS, CAT, and SOD activities showed differential responses from day 7 to day 14, 21, and 28, suggesting, in most of the cases, that La and Ce effects were counteracted (i.e., being the values at day 28 not significantly different, p > 0.05, from the relative negative controls), except for La-related ROS activities. La and Ce significantly bioconcentrated in microalgae populations up to 2- and 5-fold (i.e., at day 28 compared to day 7), in that order. Bioconcentrated La and Ce were up to 3157 and 1232 μg/g dry weight (day 28), respectively. These results suggested that low La and Ce concentrations can be slightly toxic to R. subcapitata having the potential to be bioaccumulated and potentially transferred along the food web., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The alteration of rare earth elements (REEs) biogeochemical cycles has increased the potential effects related to their environmental exposure in a one-health perspective. Cerium (Ce), gadolinium (Gd), lanthanum (La), and neodymium (Nd) are frequently related to technological applications and their environmental concentrations are already in the μg/kg - mg/kg (i.e., or L) range depending on the considered matrices. The effect of Ce, Gd, La, and Nd was investigated in a simulated AMD (0.01-10.22 mg/L) at pH 4 and 6 considering a battery of photosynthetic organisms (Raphidocelis subcapitata, Lepidium sativum, and Vicia faba) according to a multiple-endpoint approach (growth inhibition, germination index, and mutagenicity). According to modelled chemical speciation, the considered elements were mostly in the trivalent free form (86-88%) at pH 4. Gd, La, and Nd exerted the most relevant toxic effect at pH 4. The pH 6 scenario evidenced a reduction in REEs toxicity level. Mutagenicity was detected only at pH 4 by Gd (up to 3-fold compared to negative controls), La and Nd, while Ce did not show any adverse effect. Toxic effects due to Ce, Gd, La, and Nd can be reduced by controlling the pH, but several gaps of knowledge still remain about their uptake and trophic transfer, and long-term effects on targeted species., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The pervasive spread of microplastics (MPs) and nanoplastics (NPs) has raised significant concerns on their toxicity in both aquatic and terrestrial environments. These polymer-based materials have implications for plants, wildlife and human health, threatening food chain integrity and ultimate ecosystem resilience. An extensive - and growing - body of literature is available on MP- and NP-associated effects, including in a number of aquatic biota, with as yet limited reports in terrestrial environments. Effects range from no detectable, or very low level, biological effects to more severe outcomes such as (but not limited to) increased mortality rates, altered immune and inflammatory responses, oxidative stress, genetic damage and dysmetabolic changes. A well-established exposure route to MPs and NPs involves ingestion with subsequent incorporation into tissues. MP and NP exposures have also been found to lead to genetic damage, including effects related to mitotic anomalies, or to transmissible damage from sperm cells to their offspring, especially in echinoderms. Effects on the proteome, transcriptome and metabolome warrant ad hoc investigations as these integrated "omics" workflows could provide greater insight into molecular pathways of effect. Given their different physical structures, chemical identity and presumably different modes of action, exposure to different types of MPs and NPs may result in different biological effects in biota, thus comparative investigations of different MPs and NPs are required to ascertain the respective effects. Furthermore, research on MP and NP should also consider their ability to act as vectors for other toxicants, and possible outcomes of exposure may even include effects at the community level, thus requiring investigations in mesocosm models., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Friedreich's Ataxia is an autosomal recessive genetic disease causing the defective gene product, frataxin. A body of literature has been focused on the attempts to counteract frataxin deficiency and the consequent iron imbalance, in order to mitigate the disease-associated pro-oxidant state and clinical course. The present mini review is aimed at evaluating the basic and clinical reports on the roles and the use of a set of iron chelators, antioxidants and some cofactors involved in the key mitochondrial functions. Extensive literature has focused on the protective roles of iron chelators, coenzyme Q10 and analogs, and vitamin E, altogether with varying outcomes in clinical studies. Other studies have suggested mitoprotective roles for other mitochondrial cofactors, involved in Krebs cycle, such as alpha-lipoic acid and carnitine, involved in acyl transport across the mitochondrial membrane. A body of evidence points to the strong antioxidant properties of these cofactors, and to their potential contribution in mitoprotective strategies in Friedreich's Ataxia clinical evolution. Thus, we suggest the rationale for planning combination strategies based on the 3 mitochondrial cofactors and of some antioxidants and iron binders as mitoprotective cocktails in Friedreich Ataxia patients, calling attention to clinical practitioners of the importance to implement clinical trials., (Copyright © 2020 Elsevier Inc. All rights reserved.)

The vast category of microplastics in the marine environment, encompassing among other aspects their persistence, degradation and impact on biota, has become an important topic of research. In spite of environmental health concerns, much work has yet to be done on understanding the potential roles of polymer sources, composition and particle sizes in causing adverse effects which have already been observed in a number of biota. The present study was aimed at adding to current knowledge by verifying if, and to what extent, embryogenesis in the sea urchin species Paracentrotus lividus is adversely affected by polystyrene and polymethylmethacrylate virgin microparticles over a size range 1-230 μm and at concentrations of 0.1-10 mg L -1 . Developing embryos which came in contact with the microplastics only after fertilisation did not display a significant increase of developmental defects. Unlike embryo exposures, when P. lividus sperm were exposed to the microplastics or their leachates, modest, yet significant effects were observed, both in terms of decreased fertilisation rate and increase of transmissible damage to offspring. Further, it was noted that larvae more readily ingested polymethylmethacrylate than polystyrene microparticles after 3 days which may represent a route for enhancing the toxicity of the former compared to the latter. Overall, these findings provide evidence for lesser sensitivity of P. lividus early life stages to microplastics compared to other urchins such as Sphaerechinus granularis. In turn, the more robust response of P. lividus highlights the importance of choosing an appropriate test species with the highest sensitivity when investigating mildly harmful materials., (Crown Copyright © 2020. Published by Elsevier Ltd. All rights reserved.)

Heavy metal concentrations in sediments of the Gulf of Pozzuoli, GoP, and northwest of the Gulf beyond Monte di Procida, MdP, were determined. The enrichment factor, EF, revealed in GoP strong pollution with peaks for Cr and Cu of 61.1 and 96.9. High EF Cr, Cu, and Ni values were observed for MDP. Geoaccumulation index, Igeo, rates GoP extremely polluted by Cr and Cu, Igeo > 5, and MdP heavily polluted by Cr, moderately to heavily polluted by Cu, and heavily to extremely polluted by Ni. Contamination factor, Cf, was high in GoP and varied: Cu > Cr > Ni > Cd > Hg > Zn > Pb > As, and those of Cr, Cu and Ni largely surpassed the thresholds in MdP. The ecological and comprehensive ecological risk placed Cr, Cu, Hg and Ni at high or serious risk level in the Gulf, with a peak of 465 for Cu and at a moderate level in MdP except for a very high risk for Ni., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The sensitivity of the copepods Acartia tonsa, commonly used in standardized tests for environmental risk assessment and A. clausi, the dominant autochthonous congener species in the Mediterranean Sea, was assessed using sediment-derived elutriates from the industrial area of Bagnoli-Coroglio and nickel chloride as referent toxicant. Acute A. clausi naupliar immobilization test showed EC 50 for elutriates E25, E56 and E84 of 23.3%, 80.5% and >100%, respectively, compared to 59.5%, 66.6% and >100% in A. tonsa. In the 7 day sublethal test, a reduction in A. clausi egg production rates was observed in all elutriates, but only in E56 for A. tonsa. Elutriate 56, which contained the highest amount of polycyclic aromatic hydrocarbons, also induced 70% mortality in A. clausi females. Although A. clausi was more sensitive than A. tonsa, the two species had convergent responses to the three elutriates, thus opening the venue for a potential use of A. clausi in standardized ecotoxicity tests., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Two microplastic sets, polystyrene (PS) and polymethyl methacrylate (PMMA), were tested for adverse effects on early life stages of Sphaerechinus granularis sea urchins. Microparticulate PS (10, 80 and 230 μm diameter) and PMMA (10 and 50 μm diameter) were tested on developing S. granularis embryos from 10 min post-fertilisation (p-f) to the pluteus larval stage (72 h p-f), at concentrations ranging from 0.1 to 5 mg L -1 . Both PS and PMMA exposures resulted in significant concentration-related increase of developmental defects and of microplastic uptake in plutei. Moreover, embryo exposures to PS and PMMA (5 and 50 mg L -1 ) from 10 min to 5 h p-f resulted in a significant increase of cytogenetic abnormalities, expressed as significantly increased mitotic aberrations, while mitotoxicity (as % embryos lacking active mitoses) was observed in embryos exposed to PS, though not to PMMA. When S. granularis sperm suspensions were exposed for 10 min to PS or to PMMA (0.1-5 mg L -1 ), a significant decrease of fertilisation success was observed following sperm exposure to 0.1 mg L -1 PS, though not to higher PS concentrations nor to PMMA. Sperm pretreatment, however, resulted in significant offspring damage, as excess developmental defects in plutei, both following sperm exposure to PS and PMMA, thus suggesting transmissible damage from sperm pronuclei to the offspring. The overall results point to relevant developmental, cytogenetic and genotoxic effects of PS and PMMA microplastics to S. granularis early life stages, warranting further investigations of other microplastics and other target biota., (Crown Copyright © 2019. Published by Elsevier Inc. All rights reserved.)

Contamination of agricultural soils by trace elements is a recurrent hazard for human health because of the possibility of pollutants entering the food chain. Aim of this study was to assess the human health risk from consumption of the common leafy (Lactuca sativa L.) and fruit (Cucurbita pepo L.) crops, in an agricultural area of Southern Italy. Along with agricultural practices, a major pollutant source is recurrent flooding from the highly polluted Solofrana river. Soil samples and edible parts of crops from 14 sites (10 flooded and 4 not flooded) were analyzed for total amounts of As, Cd, Co, Cr, Cu, Ni, Pb, V, Zn. The bio-accumulation factor (BAF) and Health Risk Index (HRI) were calculated for each element, crop and site and as average values of all sites (BAF mean and HRI mean ). Moreover, the Hazard Index (HI) was determined for each site, as the sum of HRI for all elements. Cr and Cu, mostly derived from river flooding and agricultural practices, respectively, were the only elements whose levels exceeded law thresholds and/or the natural background of the study area. Of the two considered crops, L. sativa accumulated more Cd, Cr and Ni, whereas C. pepo was a more effective bioaccumulator of Zn. Both HRI mean (for As, Cd, Cr and Ni) and HI were higher for L. sativa than for C. pepo. A low health risk was associated to major soil pollutants (Cr and Cu) found in the study area; in contrast, combined data on soil pollution and plant bio-accumulation points to accumulation of Cd and As, mainly in lettuce, as a potential risk for human health. The results suggest that soil pollution data alone is not sufficient to assess health risk., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Soil pollution and toxicity have been investigated in the Gardanne area (southern France) at a range of sites around a recognized pollution source, a bauxite processing plant (BPP), and a power plant (PP). Soil samples were submitted to inorganic and organic analyses and tested for toxicity in two invertebrate models. Inorganic analysis was based on determining elemental concentrations by ICP-MS, encompassing a total of 26 elements including 13 rare earth elements (REEs), of the soil samples and their leachates after 24 or 48 h in seawater. Organic analyses were performed by measuring the sums of 16 polycyclic aromatic hydrocarbons (PAHs) and of total hydrocarbons (C-10 to C-40). Bioassays were carried out on the early life stages of three sea urchin species (Arbacia lixula, Paracentrotus lividus and Sphaerechinus granularis), and on a nematode (Caenorhabditis elegans). Sea urchin bioassays were evaluated by the effects of soil samples (0.1-0.5% dry wt/vol) on developing embryos and on sperm, and scored as: a) % developmental defects, b) inhibition of sperm fertilization success and offspring damage, and c) frequencies of mitotic aberrations. C. elegans 24 h-mortality assay showed significant toxicity associated with soil samples. The effects of soil samples showed heightened toxicity at two groups of sites, close to the BPP main entrance and around the PP, which was consistent with the highest concentrations found for metals and PAHs, respectively. Total hydrocarbon concentrations displayed high concentrations both close to BPP main entrance and to the PP. Further studies of the health effects of such materials in Gardanne are warranted., (Copyright © 2018. Published by Elsevier Inc.)

The extensive use of rare earth elements (REEs) in a number of technologies is expected to impact on human health, including occupational and environmental REE exposures. A body of experimental evidence on REE-associated toxicity has been accumulated in recent decades, thus providing extensive background information on the adverse effects of REE exposures. Unlike experimental studies, the consequences of REE exposures to human health have been subjected to relatively fewer investigations. Geographical studies have been conducted on residents in REE mining districts, reporting on REE bioaccumulation, and associations between REE residential exposures and adverse health effects. A recent line of studies has associated tobacco smoking and indoor smoke with increased levels of some REEs in exposed residents. A body of literature has been focused on occupational REE exposures, with the observation of respiratory tract damage. The occupations related to REE mining and processing have shown REE bioaccumulation in scalp hair, excess REE urine levels, and defective gene expression. As for other REE occupational exposures, mention should be made of: a) jobs exposing to REE aerosol, such as movie operator; b) e-waste processing and, c) diesel engine repair and maintenance, with exposures to exhaust microparticulate (containing nanoCeO 2 as a catalytic additive). Diesel exhaust microparticulate has been studied in animal models, leading to evidence of several pathological effects in animals exposed by respiratory or systemic routes. A working hypothesis for REE occupational exposures is raised on REE-based supermagnet production and manufacture, by reviewing experimental studies that suggest several pathological effects of static magnetic fields, and warrant further investigations., (Copyright © 2019. Published by Elsevier Inc.)

We studied the bioaccumulation of metals and PAHs, the pathological conditions, regressive phenomena and pathogens in wild Mytilus galloprovincialis taken along the North Pier facing the former second Italian largest steelworks of Bagnoli. There was no Cd and Pb bioaccumulation with respect to the EU role 221/2002. Metal shell index decreased as follows: Pb > Ni > Zn > Cu and correlates with the pollution state. The level of BaP was up to thirtysixfold higher the EU rule 835/2011. The sum of 4 hydrocarbons, PAH4, were up to seventeen-fold the rule. PAH levels increased toward the coast. Prevalence values of tissue necrosis and inflammatory lesions were between 50 and 100%. In May animals showed lesion like granulocytomas and inflammatory capsules. Signs of atresia, necrotic oocytes and diffused cases of hermaphroditism were detected. An appropriate localization of farming to avoid contamination from sediment turbulence and risks for consumer health is needed., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Trace elements have been acknowledged as one of the subtlest environmental hazards in all compartments of the total environment. Enhanced by activities in the anthroposphere, they accumulate in the atmosphere, lithosphere, and hydrosphere. Eventually, trace elements can bioaccumulate or biomagnifiy in the biosphere, with harmful effects on animals occupying higher trophic levels, including humans. Accordingly, there is great interest in assessing and monitoring trace element concentrations in the biosphere, and birds, especially passerines, have been commonly chosen as biomonitors. In this study, the concentration of 11 trace elements was measured (i.e. aluminum, chromium, manganese, iron, nickel, copper, zinc, arsenic, cadmium, barium, and lead) in flight feathers of Italian Sparrows, a common bird species hitherto not analysed in this respect. Samples were collected in an agricultural area in southern Italy, where a mosaic of natural environments, urbanized areas and industrial facilities can be found. Linear mixed modelling was applied to the analysis of flight feathers in juveniles, juvenile birds moulting to adulthood, and adults in three sampling years on 184 birds. Results are timely as they add new data to the scarce available information on Ba and As in bird feathers and showed clear bioaccumulation patterns from juveniles to adults for As, Cr, and Cd. Moreover, the modelling approach showed that the concentration of elements such as As, Cd and Cr can be variable across the years and that some elements, notably Cd and Ba, were inversely correlated with body mass and wing length, respectively, suggesting potential negative effects on bird health. Finally, when modelling bird body condition and trace elements, results showed that Cd and Ba negatively affect birds regardless of age or sampling year. Thus, the Italian Sparrow could be considered as a valuable biomonitor for trace elements in the total environment, especially for Cd and Ba., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Four 4-nitrophenyl-functionalized benzofuran (BF1, BF2) and benzodifuran (BDF1, BDF2) compounds were synthesized by a convenient route based on the Craven reaction. All the compounds underwent a detailed chemical-physical characterization to evaluate their structural, thermal and optical properties. An investigation on the therapeutic potential of the reported compounds was performed by analyzing their antiproliferative activity on prostatic tumour cells (PC-3). In both classes of compounds, anticancer potential is in direct correlation with the lipophilicity. From our study it emerged that antiproliferative activity was higher for benzofuran derivatives as compared to benzodifuran systems. Moreover, we report a mechanistic study relative to the most promising molecule, i.e. the apolar benzofuran BF1, that relates the antiproliferative properties found in our investigation to its ability to bind telomeric DNA (proven by CD and fluorescence techniques on tel 22 G4 DNA), and highlights its unexpected impact on cell cycle progression., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The Gulf of Pozzuoli includes the former second largest Italian steelworks of Bagnoli. The REE, Y, Th and Sc pollution in sediments of the Gulf of Pozzuoli was determined. Ce, La, Nd and Pr had the highest percentage distribution of rare earth elements normalized respect to chondrite with 31.19, 28.35, 19.51 and 8.41% individually. It was observed a marked enrichment of these elements, from west to the east from 26.39 to 111.04 mg/kg and from onshore to offshore from 31.67 to 217.74 mg/kg. The output of the principal component analysis revealed that the REE were mainly of anthropic origin being clearly linked to that of PAHs, metals and organic matter. This, together with their distribution patterns, highlighted the role of the former Bagnoli metallurgical plant in the pollution of the gulf., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Corallinales (Rhodophyta) are high Mg-calcite macroalgae and are considered among the most vulnerable organisms to ocean acidification (OA). These sensitive species play fundamental roles in coastal systems as food source and settlement promoters as well as being involved in reef stabilization, and water carbonate balance. At present only a few studies are focused on erect calcifying macroalgae under low pH/high pCO 2 and the contrasting results make difficult to predict the ecological consequences of the OA on the coralline algae. In this paper the physiological reasons behind the resistance of Jania rubens, one of the most common calcareous species, to changing ocean pH are analysed. In particular, we studied the photosynthetic and mineralogical response of J. rubens after a three-week transplant in a natural CO 2 vent system. The overall results showed that J. rubens could be able to survive under predicted pH conditions even though with a reduced fitness; nevertheless physiological limits prevent the growth and survival of the species at pH6.7. At low pH (i.e. pH7.5), the maximum and effective PSII efficiency decreased even if the increase of Rubisco expression suggests a compensation effort of the species to cope with the decreased light-driven products. In these circumstances, a pH-driven bleaching phenomenon was also observed. Even though the photosynthesis decreased at low pH, J. rubens maintained unchanged the mineralogical composition and the carbonate content in the cell wall, suggesting that the calcification process may also have a physiological relevance in addition to a structural and/or a protective role. Further studies will confirm the hypotheses on the functional and evolutionary role of the calcification process in coralline algae and on the ecological consequences of the community composition changes under high pCO 2 oceans., (Copyright © 2018 Elsevier B.V. All rights reserved.)

α-L-Rhamnosidases (α-RHAs, EC 3.2.1.40) are glycosyl hydrolases (GHs) hydrolyzing terminal α-l-rhamnose residues from different substrates such as heteropolysaccharides, glycosylated proteins and natural flavonoids. Although the possibility to hydrolyze rhamnose from natural flavonoids has boosted the use of these enzymes in several biotechnological applications over the past decades, to date only few bacterial rhamnosidases have been fully characterized and only one crystal structure of a rhamnosidase of the GH106 family has been described. In our previous work, an α-l-rhamnosidase belonging to this family, named RHA-P, was isolated from the marine microorganism Novosphingobium sp. PP1Y. The initial biochemical characterization highlighted the biotechnological potential of RHA-P for bioconversion applications. In this work, further functional and structural characterization of the enzyme is provided. The recombinant protein was obtained fused to a C-terminal His-tag and, starting from the periplasmic fractions of induced recombinant cells of E. coli strain BL21(DE3), was purified through a single step purification protocol. Homology modeling of RHA-P in combination with a site directed mutagenesis analysis confirmed the function of residues D503, E506, E644, likely located at the catalytic site of RHA-P. In addition, a kinetic characterization of the enzyme on natural flavonoids such as naringin, rutin, hesperidin and quercitrin was performed. RHA-P showed activity on all flavonoids tested, with a catalytic efficiency comparable or even higher than other bacterial α-RHAs described in literature. The results confirm that RHA-P is able to hydrolyze both α-1,2 and α-1,6 glycosidic linkages, and suggest that the enzyme may locate different polyphenolic aromatic moities in the active site., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Most of the literature reports on the impact of the former Bagnoli brownfield on the pollution of Bagnoli Bay, embedded in the Gulf of Pozzuoli (GoP). Thus, we studied concentrations, types and sources of sixteen PAHs (EPA) in sediments at 22 sites along 5 transects covering the entire area of GoP. Outstanding levels of PAHs were found, varying from 7.1μgg -1 to 2.5 E+3μgg -1 . Sediments collected at sites far away from Bagnoli were found to be polluted to a similar extent than those facing the brownfield site, with values>100μgg -1 . Total PAHs levels in the sediments of GoP were higher by thirty-eleven thousand fold than those reported by other studies from various marine sites in the world. Transit axes of fine and very fine sands and diagnostic indexes revealed a common pyrolytic PAHs pollution spreading from the Bagnoli plant to all GoP., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The distribution of metals in surface sediments of Gulf of Pozzuoli (GoP), embedding the former second Italian largest integrated steelworks of Bagnoli, was studied based on sediment dispersal, quality guidelines (SQGs) and quantitative pollution indices of the respective metals. As, Cd, Hg, Pb, Zn largely exceeded the limits. Hg had a mean of 5.8mg/kg, twentyfold higher the rule, accumulating primarily near Bagnoli site. The mean effective range quotient, m-ERM-Q, revealed a high potential for negative biological effects especially in the area nearby the Bagnoli site. The enrichment factor (EF) values were outstandingly high, >1.5 with values which were often ≥100. The geoaccumulation index, Igeo, was very critical for Cr, Cu, Hg and Ni, showing an Igeo in the range of strongly polluted (45). The principal component analysis (PCA) and Pearson's correlation matrix (CM), excluded significant contribution from weathering products., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Background: Heavy rare earth elements (HREEs) have been scarcely studied for their toxicity, in spite of their applications in several technologies. Thus HREEs require timely investigations for their adverse health effects., Methods: Paracentrotus lividus and Arbacia lixula embryos and sperm were exposed to trichloride salts of five HREEs (Dy, Ho, Er, Yb and Lu) and to Ce(III) as a light REE (LREE) reference to evaluate: 1) developmental defects (% DD) in HREE-exposed larvae or in the offspring of HREE-exposed sperm; 2) mitotic anomalies; 3) fertilization success; and 4) reactive oxygen species (ROS) formation, and nitric oxide (NO) and malondialdehyde (MDA) levels. Nominal HREE concentrations were confirmed by inductively coupled plasma mass spectrometry (ICP-MS)., Results: HREEs induced concentration-related DD increases in P. lividus and A. lixula larvae, ranging from no significant DD increase at 10 -7 M HREEs up to ≅100% DD at 10 -5 M HREE. Larvae exposed to 10 -5 M Ce(III) resulted in less severe DD rates compared to HREEs. Decreased mitotic activity and increased aberration rates were found in HREE-exposed P. lividus embryos. Significant increases in ROS formation and NO levels were found both in HREE-exposed and in Ce(III) embryos, whereas only Ce(III), but not HREEs resulted in significant increase in MDA levels. Sperm exposure to HREEs (10 -5 -10 -4 M) resulted in a concentration-related decrease in fertilization success along with increase in offspring damage. These effects were significantly enhanced for Dy(III), Ho(III), Er(III) and Yb(III), compared to Lu(III) and to Ce(III)., Conclusion: HREE-associated toxicity affected embryogenesis, fertilization, cytogenetic and redox endpoints showing different toxicities of tested HREEs., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Chondroitin sulfate is a glycosaminoglycan widely used as active principle of anti-osteoarthritis drugs and nutraceuticals, manufactured by extraction from animal cartilaginous tissues. During the manufacturing procedures, another glycosaminoglycan, the keratan sulfate, might be contemporarily withdrawn, thus eventually constituting a contaminant difficult to be determined because of its structural similarity. Considering the strict regulatory rules on the pureness of pharmaceutical grade chondrotin sulfate there is an urgent need and interest to determine the residual keratan sulfate with specific, sensitive and reliable methods. To pursue this aim, in this paper, for the first time, we set up a multi-analytical and preparative approach based on: i) a newly developed method by high performance anion-exchange chromatography with pulsed amperometric detection, ii) gas chromatography-mass spectrometry analyses, iii) size exclusion chromatography analyses coupled with triple detector array module and on iv) strong anion exchange chromatography separation. Varied KS percentages, in the range from 0.1 to 19.0% (w/w), were determined in seven pharmacopeia and commercial standards and nine commercial samples of different animal origin and manufacturers. Strong anion exchange chromatography profiles of the samples showed three or four different peaks. These peaks analyzed by high performance anion-exchange with pulsed amperometric detection and size exclusion chromatography with triple detector array, ion chromatography and by mono- or two-dimensional nuclear magnetic resonance revealed a heterogeneous composition of both glycosaminoglycans in terms of sulfation grade and molecular weight. High molecular weight species (>100 KDa) were also present in the samples that counted for chains still partially linked to a proteoglycan core., (Copyright © 2016 The Author(s). Published by Elsevier B.V. All rights reserved.)

A multidisciplinary survey was carried out on the quality of water and sediments of a coastal protected marine area, embedded between the inputs from Bagnoli steel plant to the south and a sewage plant, Volturno River and Regi Lagni channel to the north. The study integrated chemical-sedimentological data with biological and ecotoxicological analyses to assess anthropogenic pressures and natural variability. Data reveal marked differences in anthropogenic pollution between southeastern and northwestern zone, with the north affected by both inorganic and organic flows and the south influenced by levels of As, Pb and Zn in the sediments above law limits, deriving from inputs of the Bagnoli brownfield site. Meiobenthic data revealed at south higher relative abundance of sensitive species to pollution and environmental stress to the south, i.e. Lobatula lobatula and Rosalina bradyi, whereas to the north relative abundance of stress tolerant Quinqueloculina lata, Quinqueloculina pygmaea and Cribroelphidium cuvilleri were determined., (Copyright © 2016. Published by Elsevier Ltd.)

Background: Broad-ranging adverse effects are known for rare earth elements (REE), yet only a few studies tested the toxicity of several REE, prompting studies focusing on multi-parameter REE toxicity., Methods: Trichloride salts of Y, La, Ce, Nd, Sm, Eu and Gd were tested in Paracentrotus lividus sea urchin embryos and sperm for: (1) developmental defects in either REE-exposed larvae or in the offspring of REE-exposed sperm; (2) fertilization success; (3) mitotic anomalies in REE-exposed embryos and in the offspring of REE-exposed sperm, and (4) reactive oxygen species (ROS) formation, and malondialdehyde (MDA) and nitric oxide (NO) levels., Results: REEs affected P. lividus larvae with concentration-related increase in developmental defects, 10(-6) to 10(-4)M, ranking as: Gd(III)>Y(III)>La(III)>Nd(III)≅Eu(III)>Ce(III)≅Sm(III). Nominal concentrations of REE salts were confirmed by inductively coupled plasma mass spectrometry (ICP-MS). Significant increases in MDA levels, ROS formation, and NO levels were found in REE-exposed embryos. Sperm exposure to REEs (10(-5) to 10(-4)M) resulted in concentration-related decrease in fertilization success along with increase in offspring damage. Decreased mitotic activity and increased aberration rates were detected in REE-exposed embryos and in the offspring of REE-exposed sperm., Conclusion: REE-associated toxicity affecting embryogenesis, fertilization, cytogenetic and redox endpoints showed different activities of tested REEs. Damage to early life stages, along with redox and cytogenetic anomalies should be the focus of future REE toxicity studies., (Copyright © 2016 Elsevier Inc. All rights reserved.)

Background: A number of applications have been developed using rare earth elements (REE), implying several human exposures and raising unsolved questions as to REE-associated health effects., Methods: A MedLine survey was retrieved from early reports (1980s) up to June 2015, focused on human and animal exposures to REE. Literature from animal models was selected focusing on REE-associated health effects., Results: Some REE occupational exposures, in jobs such as glass polishers, photoengravers and movie projectionists showed a few case reports on health effects affecting the respiratory system. No case-control or cohort studies of occupational REE exposures were retrieved. Environmental exposures have been biomonitored in populations residing in REE mining areas, showing REE accumulation. The case for a iatrogenic REE exposure was raised by the use of gadolinium-based contrast agents for nuclear magnetic resonance. Animal toxicity studies have shown REE toxicity, affecting a number of endpoints in liver, lungs and blood. On the other hand, the use of REE as feed additives in livestock is referred as a safe and promising device in zootechnical activities, possibly suggesting a hormetic effect both known for REE and for other xenobiotics. Thus, investigations on long-term exposures and observations are warranted., Conclusion: The state of art provides a limited definition of the health effects in occupationally or environmentally REE-exposed human populations. Research priorities should be addressed to case-control or cohort studies of REE-exposed humans and to life-long animal experiments., (Copyright © 2015 Elsevier Inc. All rights reserved.)

Accumulating evidence shows an association between deregulation of miRNAs and exposure to environmental chemicals; miRNAs play a unique regulatory role in gene expression. Among environmental pollutants, dioxins are a family of compounds that are known to have multiple hazardous effects. Also, in utero exposure of the fetus to dioxins has been shown to cause impaired psychomotor development, decreased immune function and skin disease. miR-191 is a microRNA that has been found to be up-regulated by dioxin in hepatocellular carcinoma cells in vitro. Our study provides the first molecular evidence in vivo of a positive relationship between levels of polychlorinated biphenyls (PCBs) and miR-191 expression in human peripheral blood mononuclear cells. miR-191 expression was significantly correlated with blood concentrations of total PCB and, in particular, of 3,3',4,4',5,5'-hexachlorobiphenyl (PCB 169, a coplanar congener). Blood concentrations of PCB 169 correlated significantly with miR-191 expression in pregnant women living in a PCB-polluted area, who underwent therapeutic abortion due to fetal malformations. These data suggest that miRNAs could be potential biomarkers to clarify the mechanisms of environmental disease., (Copyright © 2013 Elsevier B.V. All rights reserved.)