Effects of TiO2 ultraviolet filter and sunscreens on coastal dune plant performance and competitive interactions.

Ultraviolet filters (UVFs) added to sunscreens (SS) are emerging contaminants in marine environments due to their adverse effects on organisms and ecosystems. UVFs have also been detected in beach-dune systems, but their influence on resident organisms has not been explored yet. Native plants are fundamental components of coastal dunes, and these ecologically/economically important systems are currently among the most threatened globally. Thus, understanding whether UVFs may act as threats to dune plants is crucial. This field study evaluated and compared the effects of titanium dioxide nanoparticles (nTiO2), one of the inorganic UVFs most commonly added to sunscreens, and those of a commercial sunscreen product containing it (SS-nTiO2) on the performance of adult dune plants of a native (Thinopyrum junceum) and a non-native invasive species (Carpobrotus sp. pl.) and their competitive interactions at environmentally realistic concentrations. The effects of nTiO2, SS-nTiO2 and of a sunscreen product containing just organic UVFs (SS-OF) on early life stages of T. junceum were also examined. Ti bulk content in sand and plants at the study site ranged from 970 to 1069 mg kg-1 and from 2 to 7.9 mg kg-1, respectively. Thinopyrum junceum adult plants periodically exposed during the summer season to seawater contaminated by SS-nTiO2 produced less biomass than un-exposed plants and nTiO2 exposed plants. nTiO2 and SS-nTiO2 reduced the capacity of T. junceum to control the spread of Carpobrotus. Both SS-nTiO2 and SS-OF reduced seedling emergence in T. junceum whereas nTiO2 did not. These results demonstrated that the periodical exposures of native dune plants to sunscreens could reduce their establishment success and growth and favor invasive plant spread potentially resulting in community structure changes. They also emphasize the need to assess the phytotoxicity not only of single UVFs but especially that of complete sunscreen products to design more eco-friendly formulations in the future.

New geochemical data for defining origin and distribution of mercury in groundwater of a coastal area in southern Tuscany (Italy).

A geochemical study was conducted in a coastal plain in the Orbetello Lagoon area in southern Tuscany (Italy), acquiring new data on groundwater, lagoon water, and stream sediment for insights into the origin, distribution, and behaviour of mercury in a Hg-enriched carbonate aquifer. The main hydrochemical features of the groundwater are ruled by the mixing of Ca-SO4 and Ca-Cl continental fresh waters of the carbonate aquifer and Na-Cl saline waters of the Tyrrhenian Sea and Lagoon of Orbetello. Groundwater had highly variable Hg concentrations (< 0.1-11 µg/L) that were not correlated with the percentage of saline water, depth in the aquifer, or distance from the lagoon. This excluded the possibility that saline water could be the direct source of Hg in groundwater and responsible for release of the element through interaction with the carbonate lithologies of the aquifer. The origin of Hg in groundwater could be ascribed to the Quaternary continental sediments overlying the carbonate aquifer because i) high Hg concentrations were found in the continental sediments of the coastal plain and in the contiguous lagoon sediments; ii) waters from the upper part of aquifer had the highest Hg concentrations; iii) Hg levels in groundwater increased with increasing thickness of the continental deposits. The high Hg content in the continental and lagoon sediments is geogenic due to regional and local Hg anomalies and to sedimentary and pedogenetic processes. It can be assumed that i) water circulating in these sediments dissolves the solid Hg-bearing constituents and mobilises this element mainly as chloride complexes; ii) Hg-enriched water moves from the upper part of the carbonate aquifer due to the cone of depression generated by intense pumping of groundwater by fish farms in the study area.

Sensitivity of Hydra vulgaris to Nanosilver for Environmental Applications.

Nanosilver applications, including sensing and water treatment, have significantly increased in recent years, although safety for humans and the environment is still under debate. Here, we tested the environmental safety of a novel formulation of silver nanoparticles functionalized with citrate and L-cysteine (AgNPcitLcys) on freshwater cnidarian Hydra vulgaris as an emerging ecotoxicological model for the safety of engineered nanomaterials. AgNPcitLcys behavior was characterized by dynamic light scattering (DLS), while Ag release was measured by inductively coupled plasma mass spectrometry (ICP-MS). H. vulgaris (n = 12) subjects were evaluated for morphological aberration after 96 h of exposure and regeneration ability after 96 h and 7 days of exposure, after which the predatory ability was also assessed. The results show a low dissolution of AgNPcitLcys in Hydra medium (max 0.146% of nominal AgNPcitLcys concentration) and highlight a lack of ecotoxicological effects, both on morphology and regeneration, confirming the protective role of the double coating against AgNP biological effects. Predatory ability evaluation suggests a mild impairment of the entangling capacity or of the functionality of the tentacles, as the number of preys killed but not ingested was higher than the controls in all exposed animals. While their long-term sub-lethal effects still need to be further evaluated on H. vulgaris, AgNPcitLcys appears to be a promising tool for environmental applications, for instance, for water treatment and sensing.

Ecologically based methods for promoting safer nanosilver for environmental applications.

Nanosilver, widely employed in consumer products as biocide, has been recently proposed as sensor, adsorbent and photocatalyst for water pollution monitoring and remediation. Since nanosilver ecotoxicity still pose limitations to its environmental application, a more ecological exposure testing strategy should be coupled to the development of safer formulations. Here, we tested the environmental safety of novel bifunctionalized nanosilver capped with citrate and L-cysteine (AgNPcitLcys) as sensor/sorbent of Hg2+ in terms of behaviour and ecotoxicity on microalgae (1-1000 µg/L) and microcrustaceans (0.001-100 mg/L), from the freshwater and marine environment, in acute and chronic scenarios. Acute toxicity resulted poorly descriptive of nanosilver safety while chronic exposure revealed stronger effects up to lethality. Low dissolution of silver ions from AgNPcitLcys was observed, however a nano-related ecotoxicity is hypothesized. Double coating of AgNPcitLcys succeeded in mitigating ecotoxicity to tested organisms, hence encouraging further research on safer nanosilver formulations. Environmentally safe applications of nanosilver should focus on ecologically relevant exposure scenarios rather than relying only on acute exposure data.

Biochar Amendment Reduces the Availability of Pb in the Soil and Its Uptake in Lettuce.

The aim of this study was to investigate the ability of biochar amendment to reduce the availability of Pb in the soil and its uptake in lettuce (Lactuca sativa L. var. adela). Seedlings of lettuce were cultivated in Pb-contaminated soils, both with and without 5% biochar (w/w), as well as in a simplified soilless system (hydroponics) at the ecologically relevant Pb concentration of 100 µM, both with and without 1% biochar. Soils amended with biochar resulted in a ca. 50% reduction of the extractable (bioavailable) fraction of Pb, limiting the accumulation of this toxic element in the leaves of lettuce by ca. 50%. A similar behavior was observed for lettuce plants grown hydroponically, even with a much higher reduction of Pb uptake (ca. 80%). Increased cation exchange capacity and pH were likely the main factors limiting the bioavailability of Pb in the soil. Complexation with functional groups and precipitation/co-precipitation both on the biochar surface and in soil aggregates were likely the main mechanisms immobilizing this element.

Cellular Responses Induced by Zinc in Zebra Mussel Haemocytes. Loss of DNA Integrity as a Cellular Mechanism to Evaluate the Suitability of Nanocellulose-Based Materials in Nanoremediation.

Zinc environmental levels are increasing due to human activities, posing a threat to ecosystems and human health. Therefore, new tools able to remediate Zn contamination in freshwater are highly recommended. Specimens of Dreissena polymorpha (zebra mussel) were exposed for 48 h and 7 days to a wide range of ZnCl2 nominal concentrations (1-10-50-100 mg/L), including those environmentally relevant. Cellulose-based nanosponges (CNS) were also tested to assess their safety and suitability for Zn removal from freshwater. Zebra mussels were exposed to 50 mg/L ZnCl2 alone or incubated with 1.25 g/L of CNS (2 h) and then removed by filtration. The effect of Zn decontamination induced by CNS has been verified by the acute toxicity bioassay Microtox®. DNA primary damage was investigated by the Comet assay; micronuclei frequency and nuclear morphological alterations were assessed by Cytome assay in mussels' haemocytes. The results confirmed the genotoxic effect of ZnCl2 in zebra mussel haemocytes at 48 h and 7-day exposure time. Zinc concentrations were measured in CNS, suggesting that cellulose-based nanosponges were able to remove Zn(II) by reducing its levels in exposure waters and soft tissues of D. polymorpha in agreement with the observed restoration of genetic damage exerted by zinc exposure alone.

Alginate coating modifies the biological effects of cerium oxide nanoparticles to the freshwater bivalve Dreissena polymorpha.

The adsorption of biomacromolecules is a fundamental process that can alter the behaviour and adverse effects of nanoparticles (NPs) in natural systems. While the interaction of NPs with natural molecules present in the environment has been described, their biological impacts are largely unknown. Therefore, this study aims to provide a first evidence of the influence of biomolecules sorption on the toxicity of cerium oxide nanoparticles (CeO2NPs) towards the freshwater bivalve Dreissena polymorpha. To this aim, we compared naked CeO2NPs and coated with alginate and chitosan, two polysaccharides abundant in aquatic environments. Mussels were exposed to the three CeO2NPs (naked, chitosan- and alginate-coated) up to 14 days at 100 µg L-1, which is a concentration higher than the environmental one predicted for this type of NP. A suite of biomarkers related to oxidative stress and energy metabolism was applied, and metabolomics was also carried out to identify metabolic pathways potentially targeted by CeO2NPs. Results showed that the coating with chitosan reduced NP aggregation and increased the stability in water. Nonetheless, the Ce accumulation in mussels was similar in all treatments. As for biological effects, all three types of CeO2NPs reduced significantly the level of reactive oxygen species and the activity of superoxide dismutase, glutathione peroxidase and glutathione-S-transferase. The effect was more pronounced in individuals exposed to CeO2NPs coated with alginate, which also significantly induced the activity of the electron transport system. Metabolomics analysis of amino acid metabolism showed modulation only in mussels treated with CeO2NPs coated with alginate. In this group, 25 metabolites belonging to nucleotides, lipids/sterols and organic osmolytes were also modulated, suggesting that the nanoparticles affect energetic metabolism and osmoregulation of mussels. This study highlights the key role of the interaction between nanoparticles and natural molecules as a driver of nanoparticle ecotoxicity.

Coating with polysaccharides influences the surface charge of cerium oxide nanoparticles and their effects to Mytilus galloprovincialis.

This study focused on the effects of surface coating, acquired through the interaction with natural biomolecules, on the behavior and ecotoxicity of nanoparticles (NPs). To this aim, the effects of Cerium Oxide Nanoparticles (CeO2NPs) naked and coated with chitosan and alginate on the marine mussel Mytilus galloprovincialis were compared. Mussels were exposed for 7 days to 100 µg L-1 of CeO2NPs and for 28 days to 1 µg L-1 of CeO2NPs. In both experiments CeO2NPs were used naked and coated with the two polysaccharides. The lowest tested concentration allowed to understand the environmental relevance of this biological process. A set of biomarkers related to oxidative stress/damage and energy metabolism was applied to assess the ecotoxicity of CeO2NPs. The aggregation and stability in water of CeO2NPs were measured through dynamic light scattering analysis and the levels of Ce in the exposure media and in mussels soft tissues were determined by inductively coupled plasma-mass spectrometry. Results showed a different hydrodynamic behavior and stability of CeO2NPs in saltwater related to the different coatings. Despite this, no differences in the bioaccumulation of CeO2NPs were observed among the experimental groups. Different coatings affected also CeO2NPs toxicological outcomes in both 7- and 28-days exposures. Coating with chitosan enhanced antioxidant enzyme activities while coating with alginate triggered oxidative damage. Although the oxidant pathways did not differ that much among the exposures, biomarkers of energetic supplies suggested a different strategy of defense in response to CeO2NP exposure at a lower concentration and for a longer period of time. The obtained results are in line with findings of a previous study on freshwater mussels, suggesting that the coating with biomolecules, which impart negative charge to the NPs, might enhance their biological effects. This study highlighted that interactions of NPs with natural biomolecules largely present in the aquatic environment could affect NPs toxicity altering the interaction towards organisms.

Effect-Based Approach to Assess Nanostructured Cellulose Sponge Removal Efficacy of Zinc Ions from Seawater to Prevent Ecological Risks.

To encourage the applicability of nano-adsorbent materials for heavy metal ion removal from seawater and limit any potential side effects for marine organisms, an ecotoxicological evaluation based on a biological effect-based approach is presented. ZnCl2 (10 mg L-1) contaminated artificial seawater (ASW) was treated with newly developed eco-friendly cellulose-based nanosponges (CNS) (1.25 g L-1 for 2 h), and the cellular and tissue responses of marine mussel Mytilus galloprovincialis were measured before and after CNS treatment. A control group (ASW only) and a negative control group (CNS in ASW) were also tested. Methods: A significant recovery of Zn-induced damages in circulating immune and gill cells and mantle edges was observed in mussels exposed after CNS treatment. Genetic and chromosomal damages reversed to control levels in mussels' gill cells (DNA integrity level, nuclear abnormalities and apoptotic cells) and hemocytes (micronuclei), in which a recovery of lysosomal membrane stability (LMS) was also observed. Damage to syphons, loss of cilia by mantle edge epithelial cells and an increase in mucous cells in ZnCl2-exposed mussels were absent in specimens after CNS treatment, in which the mantle histology resembled that of the controls. No effects were observed in mussels exposed to CNS alone. As further proof of CNS' ability to remove Zn(II) from ASW, a significant reduction of >90% of Zn levels in ASW after CNS treatment was observed (from 6.006 to 0.510 mg L-1). Ecotoxicological evaluation confirmed the ability of CNS to remove Zn from ASW by showing a full recovery of Zn-induced toxicological responses to the levels of mussels exposed to ASW only (controls). An effect-based approach was thus proven to be useful in order to further support the environmentally safe (ecosafety) application of CNS for heavy metal removal from seawater.

Bifunctionalized Silver Nanoparticles as Hg2+ Plasmonic Sensor in Water: Synthesis, Characterizations, and Ecosafety.

In this work, hydrophilic silver nanoparticles (AgNPs), bifunctionalized with citrate (Cit) and L-cysteine (L-cys), were synthesized. The typical local surface plasmon resonance (LSPR) at λ max = 400 nm together with Dynamic Light Scattering (DLS) measurements (<2RH> = 8 ± 1 nm) and TEM studies (Ø = 5 ± 2 nm) confirmed the system nanodimension and the stability in water. Molecular and electronic structures of AgNPs were investigated by FTIR, SR-XPS, and NEXAFS techniques. We tested the system as plasmonic sensor in water with 16 different metal ions, finding sensitivity to Hg2+ in the range 1-10 ppm. After this first screening, the molecular and electronic structure of the AgNPs-Hg2+ conjugated system was deeply investigated by SR-XPS. Moreover, in view of AgNPs application as sensors in real water systems, environmental safety assessment (ecosafety) was performed by using standardized ecotoxicity bioassay as algal growth inhibition tests (OECD 201, ISO 10253:2006), coupled with determination of Ag+ release from the nanoparticles in fresh and marine aqueous exposure media, by means of ICP-MS. These latest studies confirmed low toxicity and low Ag+ release. Therefore, these ecosafe AgNPs demonstrate a great potential in selective detection of environmental Hg2+, which may attract a great interest for several biological research fields.

Trace Element Uptake and Accumulation in the Medicinal Herb Hypericum perforatum L. Across Different Geolithological Settings.

The worldwide growing interest in traditional medicines, including herbal medicines and herbal dietary supplements, has recently been accompanied by concerns on quality and safety of this type of health care. The content of nutritional and potentially toxic elements in medicinal plants is of paramount interest as it may vary remarkably according to different environmental and ecophysiological factors. In this study, the concentrations of essential and non-essential trace elements-Co, Cr, Cu, Ni, Sr, and Zn-were determined in the roots and aerial parts of the worldwide distributed and economically important medicinal herb Hypericum perforatum L. (St. John's wort) and in its growing substrate. Most of the analyzed trace elements varied considerably in the plant parts according to edaphic conditions and soil geochemistry. However, uptake and retention in H. perforatum compartments of Co, Cr, and Ni, which markedly differentiated the investigated soils, were controlled by excluding mechanisms of the plant. Despite this, the Ni concentrations in the aerial parts, commonly used in herbal preparations, of H. perforatum plants from serpentine soils were not insignificant in relation to eventual human consumption. Good practice to assure the herbal product quality of H. perforatum collected from the wild cannot ignore the thorough understanding of the geolithological and geochemical features of the harvesting areas.

Influence of ore processing activity on Hg, As and Sb contamination and fractionation in soils in a former mining site of Monte Amiata ore district (Italy).

A geochemical study was carried out at the former Abbadia San Salvatore (ASS) mining site of the Monte Amiata ore district (Italy). Hg, As and Sb total contents and fractionation using a sequential extraction procedure were determined in soil and mining waste samples. Ore processing activities provided a different contribution to Hg contamination and concentration in soil fractions, influencing its behaviour as volatility and availability. Soils of roasting zone showed the highest Hg contamination levels mainly due to the deposition of Hg released as Hg0 by furnaces during cinnabar roasting. High Hg contents were also measured in waste from the lower part of mining dump due to the presence of cinnabar. The fractionation pattern suggested that Hg was largely as volatile species in both uncontaminated and contaminated soils and mining waste, and concentrations of these Hg species increased as contamination increased. These findings were in agreement with the fact that the ASS mining site is characterized by high Hg concentrations in the air and the presence of Hg0 liquid droplets in soil. Volatile Hg species were also prevalent in uncontaminated soils likely because the Monte Amiata region is an area characterized by anomalous fluxes of gaseous Hg from natural and anthropogenic inputs. At the ASS mining site soils were also contaminated by Sb, while As contents were comparable with its local background in soil. In all soil and waste samples Sb and As were preferentially in residual fraction.

Chemical and biological methods to evaluate the availability of heavy metals in soils of the Siena urban area (Italy).

A biogeochemistry field study was conducted in the Siena urban area (Italy) with the main objective of establishing the relationship between available amounts of heavy metals in soil assessed by a chemical method (soil fractionation) and bioavailability assessed by a biological method (bioaccumulation in earthworm tissues). The total content of traffic-related (Cd, Cu, Pb, Sb, Zn) and geogenic (Co, Cr, Ni, U) heavy metals in uncontaminated and contaminated soils and their concentrations in soil fractions and earthworms were used for this purpose. The bioavailability of heavy metals assessed by earthworms did not always match the availability defined by soil fractionation. Earthworms were a good indicator to assess the bioavailability of Pb and Sb in soil, while due to physiological mechanisms of regulation and excretion, Cd, Cu and Zn tissue levels in these invertebrates gave misleading estimates of their bioavailable pool. No relationship was identified between chemical and biological availability for the geogenic heavy metals, characterized by a narrow range of total contents in soil. The study highlighted that chemical and biological methods should be combined to provide more complete information about heavy element bioavailability in soils.

Potentially toxic element contamination in soil and accumulation in maize plants in a smelter area in Kosovo.

A biogeochemical field study was carried out in the industrial area of Kosovska Mitrovica in northern Kosovo, where agricultural soils were contaminated by potentially toxic elements due to smelting activity. Total and bioavailable contents of As, Cd, Co, Cu, Pb, Sb, U and Zn in soil and their concentrations in maize roots and grains were determined. Soil contamination by As, Cd, Cu, Pb, Sb and Zn was variable from slightly to highly contaminated soils and influenced both the bioavailable fraction and accumulation of these potentially toxic elements in maize tissues. The comparison between potentially toxic element concentrations in roots and grains indicated that maize is able to limit the transfer of non-essential elements to edible parts. The plant-to-soil bioconcentration indices suggested that the transfer of potentially toxic elements from soil to plant was predicted better by bioavailable concentrations than by the total contents. These indices further identified some competitions and interactions among these elements in root uptake and root-to-grain translocation.

Heavy element accumulation in Evernia prunastri lichen transplants around a municipal solid waste landfill in central Italy.

This paper presents the results of a biomonitoring study to evaluate the environmental impact of airborne emissions from a municipal solid waste landfill in central Italy. Concentrations of 11 heavy elements, as well as photosynthetic efficiency and cell membrane integrity were measured in Evernia prunastri lichens transplanted for 4months in 17 monitoring sites around the waste landfill. Heavy element contents were also determined in surface soils. Analytical data indicated that emissions from the landfill affected Cd, Co, Cr, Cu, Ni, Pb, Sb and Zn concentrations in lichens transplanted within the landfill and along the fallout direction. In these sites moderate to severe accumulation of these heavy elements in lichens was coupled with an increase in cell membrane damage and decrease in photosynthetic efficiency. Nevertheless, results indicated that landfill emissions had no relevant impact on lichens, as heavy element accumulation and weak stress symptoms were detected only in lichen transplants from sites close to solid waste. The appropriate management of this landfill poses a low risk of environmental contamination by heavy elements.

Effects of landfill leachate treatment on hepatopancreas of Armadillidium vulgare (Crustacea, Isopoda).

The major environmental impact of landfills is emission of pollutants via the leachate and gas pathways. The hepatopancreas of the terrestrial isopod Armadillidium vulgare (Isopoda, Crustacea, Latreille 1804) plays an important role in the bioaccumulation of contaminants, such as heavy metals. To evaluate the effects of landfill leachate treatment, 2 different approaches were applied: 1) the detection of accumulation of trace elements (As, Cd, Cr, Cu, Sb, Zn, Pb, Ni, V) in hepatopancreatic cells, and 2) the evaluation of biological effect of contaminants on fresh hepatopancreatic cells by flow-cytometric analyses. The presence of 2 different cell types (herein referred to as "small" [S] cells and "big" [B] cells, in agreement with the literature based on morphological examinations) was detected for the first time by flow cytometry, which also highlighted their different response to stress stimuli. In particular, B cells appeared more sensitive to landfill leachate treatment, being more damaged in the short term, while S cells seemed more adaptive. Furthermore, S cells could represent a pool from which they are able to differentiate into B cells. These findings were also confirmed by principal component analyses, underlining that S SYBR Green I bright cells correlate with specific chemicals (Ca, Cu, Co), confirming their resistance to stress stimuli, and suggesting that the decrease of specific cell types may prime other elements to replace them in a homeostasis-preservation framework.

Trace element distribution and 235U/238U ratios in Euphrates waters and in soils and tree barks of Dhi Qar province (southern Iraq).

To assess the quality of the environment in southern Iraq after the Gulf War II, a geochemical survey was carried out. The survey provided data on the chemistry of Euphrates waters, as well as the trace element contents, U and Pb isotopic composition, and PAH levels in soil and tree bark samples. The trace element concentrations and the (235)U/(238)U ratio values in the Euphrates waters were within the usual natural range, except for the high contents of Sr due to a widespread presence of gypsum in soils of this area. The trace element contents in soils agreed with the common geochemistry of soils from floodplain sediments. Some exceptions were the high contents of Co, Cr and Ni, which had a natural origin related to ophiolitic outcrops in the upper sector of the Euphrates basin. The high concentrations of S and Sr were linked to the abundance of gypsum in soils. A marked geochemical homogeneity of soil samples was suggested by the similar distribution pattern of rare earth elements, while the (235)U/(238)U ratio was also fairly homogeneous and within the natural range. The chemistry of the tree bark samples closely reflected that of the soils, with some notable exceptions. Unlike the soils, some tree bark samples had anomalous values of the (235)U/(238)U ratio due to mixing of depleted uranium (DU) with the natural uranium pool. Moreover, the distribution of some trace elements (such as REEs, Th and Zr) and the isotopic composition of Pb in barks clearly differed from those of the nearby soils. The overall results suggested that significant external inputs occurred implying that once formed the DU-enriched particles could travel over long distances. The polycyclic aromatic hydrocarbon concentrations in tree bark samples showed that phenanthrene, fluoranthene and pyrene were the most abundant components, indicating an important role of automotive traffic.

Environmental distribution of uranium and other trace elements at selected Kosovo sites.

This paper reports the results of a study using lichens as biomonitors to investigate the environmental distribution of uranium and other trace elements at selected Kosovo sites. The results suggested that the use of depleted uranium (DU) ammunitions in Kosovo did not cause a diffuse environmental contamination in such a way to have caused a detectable U enrichment in lichens. Also isotopic (235)U/(238)U measurements did not indicate the presence of DU particles in lichens. The present results also provided no indication of intense environmental contamination by the other trace elements analyzed, with the exception of Kosovska Mitrovica, where a diffuse environmental contamination by several heavy elements such as Pb, Zn, As and Cd was found.