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Nano-zero-valent iron (nZVI) and activated carbon (AC) addition are ongoing techniques for the remediation of hydrophobic organic compound-contaminated sediment and water, but with still unexplored eco(toxico)logical implications, especially when applied in situ. In this study, we investigated AC and nZVI as remediation methods for marine contaminated sediment and water, including chemical and toxicity (Artemia franciscana survival and genotoxicity) surveys. The removal efficiency of AC and nZVI (about 99%) was similar in both sediment and seawater, while the survival of nauplii and adults was mainly impacted by nZVI than AC. At the molecular level, the nZVI-addition induced down-regulation in the expression of two stress and one developmental genes, whereas AC was able to up-regulated only one gene involved in stress response. Results suggested that the use of AC is safer than nZVI that requires further investigation and potential optimization to reduce secondary undesired effects. Graphical abstract

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.

Nano Zero-Valent Iron (nZVI) and Activated Carbon (AC) addition is recently developed techniques applied for the remediation of sediments and aqueous solutions contaminated with hydrophobic organic compounds. However, an important point that must be underlined consists in the possible occurrence of eco(toxico)logical secondary effects, especially when applied in situ. In this study, we investigated AC and nZVI as remediation methods in contaminated water and sediment, evaluating also their possible negative impact on marine crustacean Artemia franciscana. The results showed that the AC and nZVI efficiency removal were similar for both sediment and seawater; and the survival of both nauplii and adults was mainly impacted by nZVI than by AC. At the molecular level, the nZVI-addition induced variations in the expression of stress and developmental genes. In conclusion, these data suggest potential ecotoxicological effects of nZVI and stress the need for a detailed further investigation of secondary effects of this technique.

We present experimental data on water repetitively brought in contact with cellophane. Although this hydrophilic polymer is insoluble in water, repetitively immersing it in water changes the liquid’s properties. We compare the physicochemical properties of the water left over after removing the cellophane to those of previously published data on water repetitively brought in contact with other in water insoluble polymers (cotton wool or Nafion). Some of the properties are similar. All the properties considerably differ from those of the Milli-Q® water used. On lyophilizing these waters, solid residues remain. The residues are soluble in water. The chemical nature of the residues differs from that of the perturbing polymers.

The production of rare earth elements, REE, has significantly increased over the past years, in parallel with the latest advances in nanotechnologies and representing a new group of emerging contaminants. They find application in construction, transport, agriculture, electronics, catalysis, and biomedicine. Their extraordinary intrinsic characteristics are fundamental for overcoming current technological challenges. The accumulation of REE is consistent in near-shore waters being affected by runoff, wastewater discharge, and proximity to built-up areas. Bioavailability in water, sediments, and accumulation in marine biota as well their endocrine disruptor effect is mostly unknown. There is a significant gap of knowledge on the ecotoxicological behaviour of REE in marine areas. The existing investigations have been performed inside well-mixed estuarine systems, due to complex hydrodynamics and multiple sediment transport situations. This hampers the definition of regulatory thresholds for REE concentrations and emissions. The review summarizes the existing information on REE geochemistry and physicochemical conditions influencing dissolution, surface complexation reactions, and distribution at the continent–ocean interface, as well as their speciation, bioavailability, and detrimental effects on living organisms. Strategies for reducing REE usage and inputs are also discussed.

Rare earth elements (REEs) are recognized as emerging contaminants with implications in human and environmental health. Apart from their adverse effects, REEs have been reported as having positive effects when amended to fertilizers and livestock feed additives, thus suggesting a hormetic trend, implying a concentration-related shift from stimulation to inhibition and toxicity, with analogous trends that have been assessed for a number of xenobiotics. In view of optimizing the success of REE mixtures in stimulating crop yield and/or livestock growth or egg production, one should foresee the comparative concentration-related effects of individual REEs (e.g., Ce and La) vs. their mixtures, which may display distinct trends. The results might prompt further explorations on the use of REE mixtures vs. single REEs aimed at optimizing the preparation of fertilizers and feed additives, in view of the potential recognition of their use in agronomy and zootechny., Universita degli Studi di Napoli Federico II within the CRUI-CARE Agreement, Open access funding provided by Universita degli Studi di Napoli Federico II within the CRUI-CARE Agreement.

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 (Ns and SS) and trichomes (Nt and St) 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. PM10 uptake scaled positively with SS, St and upper cuticle thickness (Tc,u) across species. PM2.5 uptake scaled positively with Tc,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 SS. We conclude that both plant surface morphological and chemical leaf traits influence PM and PAH retention, unveiling their potential role in air phytoremediation.

Polycyclic aromatic hydrocarbons (PAHs) consist of a group of over 100 different organic compounds mainly generated by anthropogenic activities. Because of their low water solubility, they tend to be accumulated in sediment, where their degradation rate is very low. Few studies have been carried out so far to investigate the effects of PAHs on Artemia franciscana. Artemia is easy to manage at laboratory scale, but it is not a sensitive biological model considering the traditional endpoints (i.e., mortality). In addition to evaluating the lethality on nauplii and adults of A. franciscana after 24 and 48 h, we focused on the genotoxicity to investigate the potential effects of phenanthrene (PHE), naphthalene (NAP), fluoranthene (FLT), and benzo(k)fluoranthene (BkF). Results showed that FLT was the most toxic both for nauplii and adults after 48 h of exposure. Real-time qPCR showed that all toxicants, including BkF, which had no negative effects on the survival of the crustacean, were able to switch the gene expression of all nine genes. This work has important ecological implications, especially on contaminated sediment assessment considering that PAHs represent the most abundant organic group of compounds in marine environment, opening new perspectives in understanding the molecular pathways activated by crustaceans.

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.

Seawater represents a potential resource to ensure sustainable availability of water for population and irrigation purposes, especially in some areas of the world. Desalination processes allow the production of fresh water, but they generate also brine as waste product. Sustainable brine management should be identified to ensure proper disposal and potentially resource recovery. This experimental study showed that emerging technologies such as Microbial Desalination Cells (MDCs) may provide a valuable contribution to the sustainability of the seawater desalination sector. In this paper, we report results on lab-scale desalination brine treatments applying MDCs, which allow energy savings, resource recovery, environmental impact minimization, and reduction of the organic load in municipal wastewater. Our results showed that MDCs’ treatment allows the removal of approximately 33 g of salts (62% of the total)—including chlorides, bromides, and sulphates—from 20 mL of brine within 96 h. The MDCs, according to the source of energy and the presence of mature biofilm at the anode, spent 7.2 J, 7.9 J, and 9.6 J in the desalination process, with the higher amount of energy required by the abiotic system and the lesser by the MDCs fed with just wastewater. Our approach also showed environmental and energy reductions because of potential metal recovery instead of returning them into marine environment. We quantified the avoided life cycle of human and marine eco-toxicity impacts as well as the reduction of cumulative energy demand of recovered metals. The main benefit in terms of avoided toxicity would arise from the mercury and copper recovery, while potential economic advantages would derive from the recovered cobalt that represents a strategic resource for many products such as battery storage systems.

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.

Sediment pollution is a major issue in coastal areas, potentially endangering human health and the marine environments. We investigated the short-term sublethal effects of sediments contaminated with polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) on the sea urchin Paracentrotus lividus for two months. Spiking occurred at concentrations below threshold limit values permitted by the law (TLVPAHs = 900 µg/L, TLVPCBs = 8 µg/L, Legislative Italian Decree 173/2016). A multi-endpoint approach was adopted, considering both adults (mortality, bioaccumulation and gonadal index) and embryos (embryotoxicity, genotoxicity and de novo transcriptome assembly). The slight concentrations of PAHs and PCBs added to the mesocosms were observed to readily compartmentalize in adults, resulting below the detection limits just one week after their addition. Reconstructed sediment and seawater, as negative controls, did not affect sea urchins. PAH- and PCB-spiked mesocosms were observed to impair P. lividus at various endpoints, including bioaccumulation and embryo development (mainly PAHs) and genotoxicity (PAHs and PCBs). In particular, genotoxicity tests revealed that PAHs and PCBs affected the development of P. lividus embryos deriving from exposed adults. Negative effects were also detected by generating a de novo transcriptome assembly and its annotation, as well as by real-time qPCR performed to identify genes differentially expressed in adults exposed to the two contaminants. The effects on sea urchins (both adults and embryos) at background concentrations of PAHs and PCBs below TLV suggest a need for further investigations on the impact of slight concentrations of such contaminants on marine biota.

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.

The shallow water benthic foraminiferal and ostracod assemblages of the Gulf of Pozzuoli, located in the central Tyrrhenian Sea, were studied to investigate the relationship between calcareous meiofaunas and contaminant concentrations in bottom sediments exposed to prolonged industrial pollution. Both benthic foraminifers and ostracods displayed high-diversity and low-dominance, unusual features in highly contaminated environments. High-diversity values were possibly linked to the oligotrophic, well-oxygenated, and CaCO3-supersaturated coastal Mediterranean waters. The comparison with historical data suggested that assemblage composition changed in the last decades, with an increase in the relative abundance of benthic foraminiferal (Quinqueloculina seminulum, Bulimina elongata) and ostracod (Xestoleberis,Loxoconcha, Semicytherura rarecostata) taxa. They probably represent organisms tolerant to the environmental variations in the last decades. The relationships between granulometry and diversity indices, high correlation values betweenQuinqueloculina lataand heavy metal pollution, and the preference of the ostracod generaUrocythereisandParacytherideafor very shallow marine waters were highlighted.

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 mu m 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., Croatian Science Foundation [IP-2018-01-5351]; Environment and Climate Change Canada, This work has been supported by the Croatian Science Foundation under grant number IP-2018-01-5351, and Environment and Climate Change Canada. the authors are grateful to Dr. Ozge Kozgus Guldu for DLS measurements.

Rare earth elements (REEs) are key constituents of modern technology and play important roles in various chemical and industrial applications. They also are increasingly used in agricultural and zootechnical applications, such as fertilizers and feed additives. Early applications of REEs in agriculture have originated in China over the past several decades with the objective of increasing crop productivity and improving livestock yield (e.g., egg production or piglet growth). Outside China, REE agricultural or zootechnical uses are not currently practiced. A number of peer-reviewed manuscripts have evaluated the adverse and the positive effects of some light REEs (lanthanum and cerium salts) or REE mixtures both in plant growth and in livestock yield. This information was never systematically evaluated from the growing body of scientific literature. The present review was designed to evaluate the available evidence for adverse and/or positive effects of REE exposures in plant and animal biota and the cellular/molecular evidence for the REE-associated effects. The overall information points to shifts from toxic to favorable effects in plant systems at lower REE concentrations (possibly suggesting hormesis). The available evidence for REE use as feed additives may suggest positive outcomes at certain doses but requires further investigations before extending this use for zootechnical purposes.

A number of aging-related disorders (ARD) have been related to oxidative stress (OS) and mitochondrial dysfunction (MDF) in a well-established body of literature. Most studies focused on cardiovascular disorders (CVD), type 2 diabetes (T2D), and neurodegenerative disorders. Counteracting OS and MDF has been envisaged to improve the clinical management of ARD, and major roles have been assigned to three mitochondrial cofactors, also termed mitochondrial nutrients (MNs), i.e., alpha-lipoic acid (ALA), Coenzyme Q10 (CoQ10), and carnitine (CARN). These cofactors exert essential-and distinct-roles in mitochondrial machineries, along with strong antioxidant properties. Clinical trials have mostly relied on the use of only one MN to ARD-affected patients as, e.g., in the case of CoQ10 in CVD, or of ALA in T2D, possibly with the addition of other antioxidants. Only a few clinical and pre-clinical studies reported on the administration of two MNs, with beneficial outcomes, while no available studies reported on the combined administration of three MNs. Based on the literature also from pre-clinical studies, the present review is to recommend the design of clinical trials based on combinations of the three MNs.

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.

Drinking water chlorination reduces the risk of pathogenic infection, but it may be harmful to human health because of trihalomethanes formation. At present, trihalomethanes concentrations are periodically monitored in fixed points along the water distribution network by in situ sampling and laboratory tests. Simulation models combined with online data sources can be useful for reproducing trihalomethanes concentrations in all part of the network and over time. The current challenge is to make reliable the model predictions. At this scope, a novel method and software system has been developed able to reproducing reliable trihalomethanes concentrations, including their species, in all parts of the water network and over time. The system has been tested on the real aqueduct Santa Sofia, disinfected by sodium hypochlorite and monitored by seven networked online multi-parameter sensors.

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.

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 EC50 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.

Exhausted woods represent a byproduct of tannin industrial production processes and their possible exploitation as a source of antioxidant compounds has remained virtually unexplored. We herein report the characterization of the antioxidant and other properties of practical interest of exhausted chestnut wood and quebracho wood, together with those of a chestnut wood fiber, produced from steamed exhausted chestnut wood. 2,2-Diphenyl-1-picrylhydrazyl (DPPH) and ferric reducing/antioxidant power (FRAP) assays indicated good antioxidant properties for all the materials investigated, with exhausted chestnut wood, and, even more, chestnut wood fiber exhibiting the highest activity. High efficiency was observed also in the superoxide scavenging assay. An increase of the antioxidant potency was observed for both exhausted woods and chestnut wood fiber following activation by hydrolytic treatment, with an up to three-fold lowering of the EC

Exhausted woods represent a byproduct of tannin industrial production processes and their possible exploitation as a source of antioxidant compounds has remained virtually unexplored. We herein report the characterization of the antioxidant and other properties of practical interest of exhausted chestnut wood and quebracho wood, together with those of a chestnut wood fiber, produced from steamed exhausted chestnut wood. 2,2-Diphenyl-1-picrylhydrazyl (DPPH) and ferric reducing/antioxidant power (FRAP) assays indicated good antioxidant properties for all the materials investigated, with exhausted chestnut wood, and, even more, chestnut wood fiber exhibiting the highest activity. High efficiency was observed also in the superoxide scavenging assay. An increase of the antioxidant potency was observed for both exhausted woods and chestnut wood fiber following activation by hydrolytic treatment, with an up to three-fold lowering of the EC50 values in the DPPH assay. On the other hand, exhausted quebracho wood was particularly effective as a nitrogen oxides (NOx) scavenger. The three materials proved able to adsorb methylene blue chosen as a model of organic pollutant and to remove highly toxic heavy metal ions like cadmium from aqueous solutions, with increase of the activity following the hydrolytic activation. These results open new perspectives toward the exploitation of exhausted woods as antioxidants, e.g., for active packaging, or as components of filtering membranes for remediation of polluted waters.

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.

Microbial Fuel Cells (MFCs) remedial technology was used for the degradation of Polycyclic Aromatic Hydrocarbons (PAHs) in marine sediments taken in front of the brownfleld steelwork facility of Bagnoli, Gulf of Pozzuoli, South Western Italy. PAHs levels were quite high and up to 30 mu g/g for fluoranthene and 0.21 mu g/g d.w. L of sediments for acenaphthene. Heavy PAHs prevailed vs light PAHs in the sediment samples before, during and after the treatment by MFCs. Different degradation rates were measured according to the complexity of each PAH, as expected. Among all PAHs, naphthalene showed after four weeks the highest degradation rate (86%), while just the 10% of Indenol[1,2,3-c,d]pyrene was degraded. MFCs achieved their highest performance in terms of Power Density (PD) after two weeks, with values ranging between 20.4 mW/m(2) and 3.17 mW/m(2) of anodic surface. CD values were normalized to the anodic surface as well, falling within a maximum of 204.8 mA/m(2) and a minimum of 9.5 mA/m(2). Even though the dynamics of PAHs degradation in MFCs and the influence of other pollutants (like metals) on MFCs performance as well as the potential mobilization of pollutants in consequence of microbial activity have to be ascertained, our preliminary results prove the high potentialities of MFCs for in-situ marine sediments remediation. (C) 2019 Elsevier Ltd. All rights reserved.

Adverse environmental conditions in the Taranto area (southern Italy) were investigated in studies of air, marine sediment, and human health. The present study aimed at providing unprecedented information on soil pollution and toxicity in a set of sites around recognized pollution sources in the Taranto area, since previous studies were focused on marine or air pollution, or on human health effects. The investigated area included a steel foundry and a power plant, as well as some sites located in an adjacent neighborhood. Surface soil samples and urban dust were collected and submitted to inorganic and organic analyses and tested for toxicity in two invertebrate bioassay models; a sea urchin (Sphaerechinus granularis) and an annelid (Caenorhabditis elegans). Inorganic analysis was carried out using ICP-MS for elemental composition for a total of 34 elements, whose levels were evaluated as a function of bioassay data analyzed through principal component analysis (PCA). Other analyses included asbestos search by powder X-ray diffraction (PXRD) and organic analysis for polycyclic aromatic hydrocarbons (PAHs) and aliphatic compounds (C10-C40). Toxicity bioassays were carried out on a sea urchin (Sphaerechinus granularis), and an annelid (Caenorhabditis elegans). Sea urchin bioassays evaluated effects of topsoil or street dust sample exposures (0.1 to 0.5% dry wt/vol) on developing embryos and on sperm, and scored as (a) % developmental defects, (b) inhibition of fertilization success and offspring damage, and (c) frequencies of mitotic aberrations. C. elegans mortality assay displayed significant toxicity associated with soil samples. The overall effects of samples showed very high toxicity at four out of nine sites. These effects were consistent with the highest levels measured for metals and PAHs. Further studies of health effects related to dust exposures in residential areas are warranted. Graphical abstract ᅟ.

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.

Wildfires have high frequency and intensity in the Mediterranean ecosystems that deeply modify the soil abiotic (i.e., pH, contents of water, organic matter and elements) and biotic properties (i.e., biomass and activity). In 2017, an intense wildfire occurred inside the Vesuvius National Park (Southern Italy), destroying approximately 50% of the existing plant cover. So, the research aimed to evaluate the fire effects on soil quality through single soil abiotic and biotic indicators and through an integrated index (SQI). To achieve the aim, soil samples were collected inside the Vesuvius National Park at 12 sampling field points before fire (BF) and after fire (AF). The findings highlighted that in AF soil, the contents of water and total carbon, element availability, respiration and the dehydrogenase activity were lower than in BF soil, in contrast, pH and hydrolase activity were significantly higher in AF soil. The microbial biomass and activity were affected by Al, Cr and Cu availability in both BF and AF soils. Despite the variations in each investigated soil abiotic and biotic property that occurred in AF soil, the overall soil quality did not significantly differ as compared to that calculated for the BF soil. The findings provide a contribution to the baseline definition of the properties and quality of burnt soil and highlight the short-term effects of fire on volcanic soil in the Mediterranean area.

The study was designed to complement the results of a previous investigation which revealed a worrying contamination scenario by polycyclic aromatic hydrocarbons, PAHs, in the Gulf of Pozzuoli, GoP, in the south of Italy. This former study also evidenced the pyrolytic source of PAHs from the dismissed metallurgical brownfield site of Bagnoli in the east side of GoP. The environmental toxicological risk assessment was also carried out. Sampling transects were drawn in the west edge of the gulf, T1 and T2, in the east side, T5, T6, in the proximity of the industrial plant and outside GoP, MdP, where pollution was expected to be low. Σ PAHs largely exceeded, from 36 up to >220 times, the regulatory standard in the east area. Lower exceeding values were determined in all the west side. FLT and PYR were the dominant hydrocarbons and PAHs distribution profiles were quite similar from west to east sides, meaning a common pollution source. Moreover, sediments appeared enriched by 4, 5 and 6 aromatic rings, 47.2%, 25.7%, and 14.0%. PAHs diagnostic ratios for source screening confirmed the pyrolytic origin of the PAH mixtures at all sites. Σ PAHcarc/ Σ PAH showed that ∼ 50% of PAHs were of carcinogenic nature at all sites. The total benzo(a)pyrene, BaP, equivalent toxicity (TEQ) values highlighted a dramatic scenario especially in the east part of GoP, with values from twenty-four fold and six hundreds fold those reported by the literature for moderate and low ecological risk environment. The output of the risk assay assessment revealed a situation of high risk in the east side of GoP, whereas a moderate to high risk level was determined throughout all GoP.

Heavy rare earth elements (HREEs) were tested for adverse effects to early life stages of the sea urchin Sphaerechinus granularis. Embryos were exposed to analytically measured HREE concentrations ranging from 10-7 to 10-5 M. No significant developmental defects (DD) increases were observed in embryos exposed to 10-7 M HREEs, whereas 10-5 M HREEs resulted in significant DD increase up to 96% for HoCl3 vs. 14% in controls. Embryos exposed to 10-6 M HREEs showed the highest DD frequency in embryos exposed to 10-6 M DyCl3 and HoCl3. Cytogenetic analysis of HREE-exposed embryos revealed a significant decrease in mitotic activity, with increases in mitotic aberrations. When S. granularis sperm were exposed to HREEs, a significant decrease of fertilization success was observed, with the offspring of sperm exposed to 10-5 M GdCl3 and LuCl3 showing significant DD increases. The results warrant investigations on HREEs in other test systems, and on REE-containing complex mixtures.

This work reports the synthesis and characterization of three novel carbazole-based push-pull dyes that have been purposely designed to be applied in p-type dye-sensitized solar cells (DSSCs). By using the same electron-donor moiety (the carbazole group) and three different electron acceptor groups, we explore how these new substituents affect the optical and electrochemical properties of the dye. State-of-the-art theoretical characterization at the DFT and TD-DFT levels of theory provides the means to understand and elucidate the connection between the chemical composition, the structure and the electronic features of these dyes. The interface between the dyes and the prototypical p-DSSC electrode (i.e. NiO) is also investigated by first-principles calculations, highlighting the importance of taking into account the dye/electrode mutual polarization for a correct alignment of the relevant electronic states (e.g., dye HOMO and NiO valence band edge). Following these characterizations, preliminary studies on the photoelectrochemical performances of the new dyes in p-DSSCs provide promising results and motivate future investigations on these new systems.

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 7.1 μg g−1 to 2.5 E +3 μg g−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 > 100 μg g−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.

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 5.8 mg/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 (4 < Igeo < 5) and very strongly polluted (Igeo > 5). The principal component analysis (PCA) and Pearson's correlation matrix (CM), excluded significant contribution from weathering products.

The influence of microelectrogenesis on PAHs degradation and detoxification operated by Pseudomonadaceae, Bacillaceae, Staphylococcaceae and Enterobacteriaceae was investigated in water environment. Single chamber, air-cathode MFCs and bioreactors were filled with the microbial pool (10(7)-10(8) CFUmL(-1)) inoculated in a 400mL Winogradsky saline solution containing no other carbon and energy source than naphthalene (80 ppm), phenanthrene (40 ppm), pyrene (40 ppm), benzo(a)pyrene (20 ppm). MFCs and bioreactors operated at 25 degrees C for thirteen weeks. Power Density (PD) and Current Density (CD) outputs as well as PAHs degradation rate were measured. The toxic effect of PAHs suspension vs.Raphidocelis subcapitata was quantified by EC1, EC20, EC50, LOEC and NOEC calculations. The results showed a significant variability in PD and CD outputs, with highest PD of 300 mW m(-3) and 25 mA m(-3). After 5 weeks, the overall PAHs concentration in MFCs decreased of a 90%. COD and TOC removal respectively of 62% and 73% after 11 weeks was achieved in MFC inoculated with bacteria (MFC2). Ecotoxicological tests showed for MFCs a lower toxic effect vs.P.subcapitata when bacteria are present. Microelectrogenesis just sped up microbial metabolism rather than take advantage from the interaction of PAHs with graphite electrodes.

Pseudomans anguilliseptica-A1 strain, isolated in an urban area, improved the efficiency of a microbial consortium, composed of Bacillaceae, Staphylococcacea, Xantomonadaceae and Enterbacteriaceae, whose ability to degrade five Polycyclic Aromatic Hydrocarbons (PAHs) among the priority pollutants was previously ascertained. Six soil microcosms were prepared with a slurry (60% soil, 40% water) artificially contaminated with anthracene (0.4 mg g-1), phenanthrene (0.2 mg g-1), naphthalene (0.2 mg g-1), pyrene (mg g-1) and benzo(a)pyrene (0.1 mg g-1) and opportunely aerated for two months. PAHs were monthly quantified by inverse phase High Performance Liquid Chromatography (HPLC), coupled with UV-Vis spectrophotometry and spectrofluorimetry. Acute toxicity assays vs Dapnia magna and Lepidium sativum, and chronic essays vs Ceriodaphnia dubia were monthly performed. Our results showed a 100% degradation for naphthalene, 99.14% for anthracene, 99.23% for phenanthrene, 86% for pyrene and 72.5% for benzo[a]pyrene after two months of treatment. A sterile P. anguilliseptica-A1 lysate in Na-K buffer added with each of the chosen PAHs (53%, wtPAHs/volsusp), operated at 30°C the oxidative degradation of naphthalene, pyrene, benzo(a)pyrene and anthracene in a few hours, while the phenanthrene enzyme degradation process took about 15 h. The GC-MS analysis revealed interesting metabolite structures such as 2- hydroxynaphthalene, 9,10-phenanthrenedione, 2,2’ diphenic acid and methyl 4-hydroxybenzoate. The direct utilization of enzymes/microbial extracts from P. anguilliseptica-A1 could present specific advantages such as availability and a fast PAHs degradation time in bioremediation processes.

WOS: 000497259100061, PubMed: 31629182, 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 mu m diameter) and PMMA (10 and 50 mu m 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., Croatian Science Foundation [IP-2018-01-5351]; Environment and Climate Change Canada, This work has been supported by the Croatian Science Foundation under project IP-2018-01-5351. Financial support from Environment and Climate Change Canada is also gratefully acknowledged. Declarations of conflict: none.

Low tech photovoltaic panels (PVPs) installed in the early ’80s are now coming to the end of their life cycle and this raises the problem of their proper disposal. As panels contain potentially toxic elements, unconventional, complex and costly procedures are required to avoid environmental health risks and in countries where environmental awareness and economic resources are limited this may be especially problematic. This work was designed to investigate potential risks from improper disposal of these panels. To accomplish this aim an exhausted panel was broken into pieces and these were placed in water for 30 days. The resulting leached solution was analyzed to determine chemical release or used in toto , to determine its potential toxicity in established tests. The end points were seed germination (on Cucumis sativus and Lens culinaris ) and effects on early development in three larval models: two crustaceans, Daphnia magna and Artemia salina , and the sea urchin Paracentrotus lividus . Our results show that the panels release small amounts of electrolytes (Na, Ca and Mg) into solution, along with antimony and manganese, with a concentration under the accepted maximum contaminant level, and nickel at a potentially toxic concentration. Developmental defects are seen in the plant and animal test organisms after experimental exposure to the whole solution leached from the broken panel. The toxic effects revealed in in vitro tests are sufficient to attract attention considering that they are exerted on both plants and aquatic animals and that the number of old PVPs in disposal sites will be very high.

Drinking water chlorination reduces the risk of pathogenic infection, but it may be harmful to human health because of disinfection by-product (DBP) formation. Available predictive models of DBP formation are almost exclusively calibrated at lab scale. The objective of the present research work is to apply two of them at full scale for the Santa Sofia aqueduct (Campania, Southern Italy), in order to predict DBP formation and evolution as function of the real water network characteristics. Live data, gathered continuously by a wireless network of multi-parametric probes, installed on the aqueduct, along with data measured in laboratory, are used for model calibration. The predictive scenarios are performed by using an open source integrated GIS-based platform (including Epanet, MSX, GIS uDig).