Metal(loid)s and Rare Earth Elements in Posidonia oceanica (L.) Delile (1813) banquettes.

The Posidonia oceanica (L.) Delile 1813 banquette provides precious ecosystem services for Mediterranean beach nourishment and protection, representing an important way of energy transfer through marine-coastal habitats. It is surprising to note how it is poorly investigated, especially concerning its double role as potential sink and source of chemicals. In particular, few studies exist about the metal (loid)s occurrence and no data are available on emerging contaminants, such as Rare Earth Elements (REEs). The present research investigated for the first time the concentrations of twenty-eight metal(loid)s and fifteen REEs in a well-structured banquette along the Italian coast (Central Tyrrhenian Sea) showing that (i) metal(loid)s and REEs occur in banquettes, with higher relative concentrations of some metal(loid)s (B, Sr, Mn, Fe, Al, Zn) and REEs (Ce, Y, La, Nd) with no statistically significant seasonal variations; (ii) Posidonia banquettes may represent an interesting biological model for chemicals monitoring.

Multigenerational tests on Daphnia spp.: a vision and new perspectives.

Multigenerational toxicity testing is a valuable tool for understanding the long-term effects of contaminants on aquatic organisms. This review focuses on the use of multigenerational tests with Daphnia, a widely used model organism in aquatic toxicological studies. The review highlights the importance of studying multiple generations to assess Daphnia spp. reproductive, growth, and physiological responses to various contaminants. We discuss the outcomes of multigenerational tests involving different contaminants, including nanoparticles, pesticides, and pharmaceuticals. The results reveal that multigenerational exposure can lead to transgenerational effects, where the impacts of contaminants are observed in subsequent generations even after the initial exposure has ceased. These transgenerational effects often manifest as reproduction, growth, and development alterations. Furthermore, we emphasize the need for standardized protocols in multigenerational testing to ensure comparability and reproducibility of results across studies. We also discuss the implications of multigenerational testing for ecological risk assessment, as it provides a more realistic representation of the long-term effects of contaminants on populations and ecosystems. Overall, this review highlights the significance of multigenerational tests with Daphnia in advancing our understanding of the ecological impacts of contaminants. Such tests provide valuable insights into the potential risks associated with long-term exposure to pollutants and contribute to the development of effective mitigation strategies for aquatic ecosystems.

A holistic picture of spatial distribution of river polluting loads in a highly anthropized area.

For many years, there has been a debate on the polluting loads affecting the Gulf of Naples, one of Italy's most spectacular and iconic landscape. The wide territory bordering the Gulf includes the Sarno river basin (SRB) managed by the Southern Apennines River Basin District Authority in the framework of Unit of Management Sarno (UoM-Sarno). The paper investigated the anthropogenic pressures and their spatial distribution in the UoM-Sarno, revealing as SRB represents a hotspot of pollution mainly due to the high population density and widespread hydro-demanding activities which are responsible of high organic and eutrophication loads. The pollution sources, variably distributed on the area, and potentially conveyed to the wastewater treatment plants (WWTPs) located into SRB, were estimated considering the WWTPs treatment capacity as well. Results revealed a holistic picture of UoM-Sarno area allowing to establish the priorities of the interventions aimed at safeguarding the coastal marine resources. In particular, 2590 tons BOD/year were directly discharged into the Gulf of Naples due to the missing of sewers, and other 10,600 tons BOD/year are potentially discharged in the Sarno river reaching the sea, considering the contribution of population, industrial activity, and livestock.

Comparison of in situ sediment remediation amendments: Risk perspectives from species sensitivity distribution.

Contaminated sediment is a major issue for aquatic environments, but attention must be kept even during remediation activities that can negatively affect resident biota especially when applied in situ. For the first time, the species sensitivity distribution (SSD) approach was applied to amendments used for in situ sediment remediation considering 39 papers including both freshwater (F) and saltwater (S) effect data (i.e. n = 17 only F, n = 19 only S, and n = 3 both F and S). Toxicity data related to the application of activated carbon (AC), nano-Zero-Valent-Iron (nZVI), apatite (A), organoclay (OC) and zeolite (Z) were collected and analyzed. SSD curves were constructed by lognormal model providing comprehensive comparisons of the sensitivities of different species to the relative testing methods. Results indicated that Bacteria were the most sensitive group of testing organisms, while Crustaceans were the less sensitive. The hazardous concentration for 5% of the affected species (HC5) were derived to determine the concentration protecting 95% of the species. OC, A and Z presented both acute and chronic toxicity. The HC5 values in descending order are: AC (4.79 g/L) > nZVI (0.02 g/L) > OC, A and Z (1.77E-04 g/L). AC and nZVI can be considered safer than OC, A and Z in sediment remediation activities, even if in situ long-term effects remained still underexplored.

Species-specific sensitivity of three microalgae to sediment elutriates.

Microalgae are considered good bioindicators of marine environmental quality. Frequently, they are used to investigate the toxicity of sediment elutriates, but their sensitivity is disputed. This paper compared the sensitivity of Phaeodactylum tricornutum (diatom), Skeletonema costatum (diatom), and Dunaliella tertiolecta (green alga), analyzing 257 samples of elutriates (1:4 sediment: water ratio), considering growth inhibition (72 h) as the reference endpoint and sediment chemical (metals, metalloids and polyaromatic hydrocarbons) and grain size. Results of the toxicity tests showed that the microalgae sensitivity was not correlated. The integration of chemical data did not allow to discriminate toxicity effects but contributed to highlight that D. tertiolecta was the most sensitive microalgae (no cell wall) followed by P. tricornutum and S. costatum. Further analysis, including lines of evidence and weight of evidence approaches to calculate risk quotients of elutriate samples, confirmed these results.

Cerium and erbium effects on Daphnia magna generations: A multiple endpoints approach.

Cerium (Ce, CeCl3) and Erbium (Er, ErCl3) are increasingly used in many electronic devices facilitating the alteration of their biogeochemical cycles (e.g. e-waste). Previous surveys stated that their environmental concentrations due to natural or anthropogenic events can reach up to 161 µg/L in ore mine effluent for Ce with a mean water concentration of 0.79 µg/L, and 11.9 µg/L for Er in ore mine effluents with a mean water concentration of 0.004 µg/L. Their potential effects onto aquatic organisms are still relatively unexplored. In this study, long-term multigenerational effects on Daphnia magna were assessed using various exposure times (3, 7, 14, and 21 days) in three generations (F0, F1 and F2). Each generation was exposed to environmental concentrations of Ce and Er (0.54 and 0.43 µg/L, respectively - mean values) and effects included organisms' size, parental reproduction, and survival, determination of reactive oxygen species (ROS), enzymatic activity (superoxide dismutase (SOD), catalase (CAT), and glutathione S-transferase (GST)), gene expression of ATP-binding cassette (ABC) transporter, and uptake. Results evidenced that chronic multi-generational exposure of daphnids to Ce and Er reduced survival, growth and reproduction, decreasing ROS, SOD and CAT from F0 to F2. Ce reduced the number of generated offsprings after each generation, while Er delayed the time of offsprings emergence, but not their number. ROS, SOD, CAT and GST evidenced that Er is slightly more toxic than Ce. Up- and downregulation of genes was limited, but Ce and Er activated the ABC transporters. Uptake of Ce and Er decreased through exposure time and generations.

Ecofriendly nanotechnologies and nanomaterials for environmental applications: Key issue and consensus recommendations for sustainable and ecosafe nanoremediation.

The use of engineered nanomaterials (ENMs) for environmental remediation, known as nanoremediation, represents a challenging and innovative solution, ensuring a quick and efficient removal of pollutants from contaminated sites. Although the growing interest in nanotechnological solutions for pollution remediation, with significant economic investment worldwide, environmental and human risk assessment associated with the use of ENMs is still a matter of debate and nanoremediation is seen yet as an emerging technology. Innovative nanotechnologies applied to water and soil remediation suffer for a proper environmental impact scenario which is limiting the development of specific regulatory measures and the exploitation at European level. The present paper summarizes the findings from the workshop: "Ecofriendly Nanotechnology: state of the art, future perspectives and ecotoxicological evaluation of nanoremediation applied to contaminated sediments and soils" convened during the Biannual ECOtoxicology Meeting 2016 (BECOME) held in Livorno (Italy). Several topics have been discussed and, starting from current state of the art of nanoremediation, which represents a breakthrough in pollution control, the following recommendations have been proposed: (i) ecosafety has to be a priority feature of ENMs intended for nanoremediation; ii) predictive safety assessment of ENMs for environmental remediation is mandatory; (iii) greener, sustainable and innovative nano-structured materials should be further supported; (iii) those ENMs that meet the highest standards of environmental safety will support industrial competitiveness, innovation and sustainability. The workshop aims to favour environmental safety and industrial competitiveness by providing tools and modus operandi for the valorization of public and private investments.

Effects of ZnO nanoparticles in the Caspian roach (Rutilus rutilus caspicus).

Most studies investigating the toxicity of zinc oxide nanoparticles (ZnO NPs) focused on the effect of size, whereas exposure concentration and duration remained poorly understood. In this study, the effect of acute and sub-acute exposures of ZnO NPs on Zn compartmentalization and biomarkers' expression were investigated in Rutilus rutilus caspicus (Caspian roach) considering various exposure scenarios: i) the assessment of the concentration-response curves and median lethal concentration (LC50); ii) the assessment of the effects of organisms exposed at LC50 value and one tenth of LC50 value of ZnO NPs suspensions for 4 d and 28 d, respectively; iii) the assessment of 14 d depuration period. The same concentrations of ZnSO4 were investigated. The highest Zn accumulation was detected in gill after sub-acute exposure (4.8 mg/L; 28 d) followed by liver, kidney and muscle. In gill, liver and muscle, Zn from Zn NPs accumulated higher concentrations. Depuration (14 d) decreased Zn content in each organ, but no complete removal occurred except for muscle. Biomarkers' activity was significantly over expressed after treatments, but depuration brought back their values to background levels and most effects were related to acute concentrations (48 mg/L; 4 d) and in presence of ZnSO4. Histopathological analyses showed that the exposure to ZnO NPs increased lesions in gill, liver and kidney, with a direct proportionality between alterations and Zn accumulated in the target organs. After depuration, lesions regressed for both ZnO NPs and ZnSO4, but not in a complete way. These data could contribute to increase the knowledge about ZnO NPs risk assessment in aquatic vertebrates, suggesting that the size of ZnO NPs can influence biomarker and histopathological effects.

Municipal wastewater spiramycin removal by conventional treatments and heterogeneous photocatalysis.

This study assessed the effects and removal options of the macrolide spiramycin, currently used for both in human and veterinary medicine- with a special focus on advanced oxidation processes based on heterogeneous TiO2_assisted photocatalysis. Spiramycin real concentrations were investigated on a seasonal basis in a municipal wastewater treatment plant (up to 35µgL-1), while its removal kinetics were studied considering both aqueous solutions and real wastewater samples, including by-products toxicity assessment. High variability of spiramycin removal by activated sludge treatments (from 9% (wintertime) to >99.9% (summertime)) was observed on a seasonal basis. Preliminary results showed that a total spiramycin removal (>99.9%) is achieved with 0.1gL-1 of TiO2 in aqueous solution after 80min. Integrated toxicity showed residual slight acute effects in the photocatalytic treated solutions, independently from the amount of TiO2 used, and could be linked to the presence of intermediate compounds. Photolysis of wastewater samples collected after activated sludge treatment during summer season (SPY 5µgL-1) allowed a full SPY removal after 80min. When photocatalysis with 0.1gL-1 of TiO2 was carried out in wastewater samples collected in winter season (SPY 30µgL-1) after AS treatment, SPY removal was up to 91% after 80min.

In situ remediation of contaminated marinesediment: an overview.

Sediment tends to accumulate inorganic and persistent hydrophobic organic contaminants representing one of the main sinks and sources of pollution. Generally, contaminated sediment poses medium- and long-term risks to humans and ecosystem health; dredging activities or natural resuspension phenomena (i.e., strongly adverse weather conditions) can remobilize pollution releasing it into the water column. Thus, ex situ traditional remediation activities (i.e., dredging) can be hazardous compared to in situ techniques that try to keep to a minimum sediment mobilization, unless dredging is compulsory to reach a desired bathymetric level. We reviewed in situ physico-chemical (i.e., active mixing and thin capping, solidification/stabilization, chemical oxidation, dechlorination, electrokinetic separation, and sediment flushing) and bio-assisted treatments, including hybrid solutions (i.e., nanocomposite reactive capping, bioreactive capping, microbial electrochemical technologies). We found that significant gaps still remain into the knowledge about the application of in situ contaminated sediment remediation techniques from the technical and the practical viewpoint. Only activated carbon-based technologies are well developed and currently applied with several available case studies. The environmental implication of in situ remediation technologies was only shortly investigated on a long-term basis after its application, so it is not clear how they can really perform.

Potential effects of TiO2 nanoparticles and TiCl4 in saltwater to Phaeodactylum tricornutum and Artemia franciscana.

Nanosized titanium dioxide (nTiO2) is widespread in many commercial products and several authors investigated its ecotoxicity effects focusing mainly on freshwater environments. Data on saltwater species are still lacking or present contradicting results. We compared for the first time the toxicity of TiCl4 and nTiO2 considering standard toxicity tests with microalgae Phaeodactylum tricornutum (growth inhibition test, 1.8-90mg/L) and crustacean Artemia franciscana (mortality test, 0.5-64mg/L). For A. franciscana, two alternative scenarios were considered beside standard protocol: i) darkness; and ii) starvation. About microalgae, results evidenced that effects of TiCl4 (EC50=63mg/L) were greater than nTiO2 (no EC50), but IC10 and IC20 were significantly lower suggesting that nTiO2 is more harmful than TiCl4 at lower concentrations. The effects of TiCl4 to crustaceans larvae in all exposure scenarios were lower compared to nTiO2 (EC50(96h)=15mg/L - standard protocol). During toxicity testing, the absence of light generally lowered nTiO2 effects while starvation increased the toxicity of both TiCl4 and nTiO2.

Effects of mineral amendments on trace elements leaching from pre-treated marine sediment after simulated rainfall events.

Bauxite extraction by-products (red mud) were used to evaluate their potential ability to stabilize trace elements from dredged and aerated/humidified marine sediment. The investigated by-products were: bauxaline®(BX) that is a press-filtered red mud; bauxsol™(BS) that is a press-filtered red mud previously washed with excess of seawater, and gypsum neutralized bauxaline® (GBX). These materials were separately mixed to dredged composted sediment sample considering 5% and 20% sediment: stabilizer ratios. For pilot experiments, rainfall events were regularly simulated for 3 months. Concentrations of As, Mo, Cd, Cr, Zn, Cu, and Ni were analyzed in collected leachates as well as toxicity. Results showed that Cd, Mo, Zn, and Cu were efficiently stabilized in the solid matrix when 20% of BX, BS, and GBX was applied. Consequently, toxicity of leachates was lower than for the untreated sediment, meaning that contaminants mobility was reduced. A 5% GBX was also efficient for Mo, Zn and Cu stabilization. In all scenarios, As stabilization was not improved. Compared to all other monitored elements, Mo mobility seemed to depend upon temperature-humidity conditions during pilot experiments suggesting the need of further investigations.

Emerging Concern from Short-Term Textile Leaching: A Preliminary Ecotoxicological Survey.

Textile dyes and their residues gained growing attention worldwide. Textile industry is a strong water consumer potentially releasing xenobiotics from washing and rinsing procedures during finishing processes. On a decentralised basis, also final consumers generate textile waste streams. Thus, a procedure simulating home washing with tap water screened cotton textiles leachates (n = 28) considering physico-chemical (COD, BOD5, and UV absorbance) and ecotoxicological data (Daphnia magna, Pseudokirchneriella subcapitata and Lepidium sativum). Results evidenced that: (i) leachates presented low biodegradability levels; (ii) toxicity in more than half leachates presented slight acute or acute effects; (iii) the remaining leachates presented "no effect" suggesting the use of green dyes/additives, and/or well established finishing processes; (iv) no specific correlations were found between traditional physico-chemical and ecotoxicological data. Further investigations will be necessary to identify textile residues, and their potential interactions with simulated human sweat in order to evidence potential adverse effects on human health.

Saltwater ecotoxicology of Ag, Au, CuO, TiO2, ZnO and C60 engineered nanoparticles: An overview.

This review paper examined 529 papers reporting experimental nanoecotoxicological original data. Only 126 papers referred to saltwater environments (water column and sediment) including a huge variety of species (n=51), their relative endpoints and engineered nanoparticles (ENPs) (n=38). We tried to provide a synthetic overview of the ecotoxicological effects of ENPs from existing data, refining papers on the basis of cross-cutting selection criteria and supporting a "mind the gap" approach stressing on missing data for hazard and risk assessment. After a codified selection procedure, attention was paid to Ag, Au, CuO, TiO2, ZnO and C60 ENPs, evidencing and comparing the observed nanoecotoxicity range of effect. Several criticisms were evidenced: i) some model organisms are overexploited like microalgae and molluscs compared to annelids, echinoderms and fish; ii) underexploited model organisms: mainly bacteria and fish; iii) exposure scenario variability: high species-specific and ENP scenarios including organism life stage and way of administration/spiking of toxicants; iv) scarce comparability between results due to exposure scenario variability; v) micro- and mesocosms substantially unexplored; vi) mixture effects: few examples are available only for ENPs and traditional pollutants; mixtures of ENPs have not been investigated yet; vii) effects of ions and ENPs: nAg, nCuO and nZnO toxicity aetiology is still a matter of discussion; viii) size and morphology effects of ENPs: scarcely investigated, justified and understood. Toxicity results evidenced that: nAu>nZnO>nAg>nCuO>nTiO2>C60.

Phytotoxicity of ionic, micro- and nano-sized iron in three plant species.

Potential environmental impacts of engineered nanoparticles (ENPs) can be understood taking into consideration phytotoxicity. We reported on the effects of ionic (FeCl3), micro- and nano-sized zerovalent iron (nZVI) about the development of three macrophytes: Lepidium sativum, Sinapis alba and Sorghum saccharatum. Four toxicity indicators (seed germination, seedling elongation, germination index and biomass) were assessed following exposure to each iron concentration interval: 1.29-1570mg/L (FeCl3), 1.71-10.78mg/L (micro-sized iron) and 4.81-33,560mg/L (nano-iron). Exposure effects were also observed by optical and transmission electron microscopy. Results showed that no significant phytotoxicity effects could be detected for both micro- and nano-sized zerovalent irons, including field nanoremediation concentrations. Biostimulation effects such as an increased seedling length and biomass production were detected at the highest exposure concentrations. Ionic iron showed slight toxicity effects only at 1570mg/L and, therefore, no median effect concentrations were determined. By microscopy, ENPs were not found in palisade cells or xylem. Apparently, aggregates of nZVI were found inside S. alba and S. saccharatum, although false positives during sample preparation cannot be excluded. Macroscopically, black spots and coatings were detected on roots of all species especially at the most concentrated treatments.

Ecotoxicity of engineered TiO2 nanoparticles to saltwater organisms: an overview.

The innovative properties of nanomaterials make them suitable for various applications in many fields. In particular, TiO2 nanoparticles (nTiO2) are widely used in paints, in cosmetics and in sunscreens that are products accessible to the mass market. Despite the great increase in the use of such nanomaterials, there is a paucity of general information about their potential effects to the aquatic species, especially to saltwater ones. Moreover, the difficulties of determining the effective exposure scenario make the acquired information low comparable. In this work, questions about the complexity of the real exposure scenario determination are discussed. The state of the art, concerning the experimental activities with nTiO2 toward the saltwater organisms is firstly illustrated, providing statistical information about the different matrices, organisms and nanoparticles employed. A comparison of the nTiO2 ecotoxicity effects, grouped by taxonomic classes, is provided illustrating their relative experimental conditions. Findings show the need to develop specific protocols for toxicity tests with ENPs to control the variability of experimental conditions. Some advices are finally proposed for the future experimental activities.

Seawater ecotoxicity of monoethanolamine, diethanolamine and triethanolamine.

Monoethanolamine (MEA), diethanolamine (DEA) and triethanolamine (TEA) are compounds with potential acute, sub-chronic and chronic toxicity effects towards aquatic species. A literature review highlighted the existence of a gap in the knowledge on their toxicity with saltwater testing species. A battery of toxicity tests including the alga Phaeodactylum tricornutum Bohlin, the bivalve molluscs Crassostrea gigas (Thunberg) and Mytilus galloprovincialis (Lmk), and the crustacean Artemia franciscana, was considered to update and improve the existing ecotoxicological information. Data were provided as the Effective Concentration that induces a 50% effect in the observed population (EC50), Lowest Observed Effect Concentration (LOEC) and No Observed Effect Concentration (NOEC). EC50, LOEC and NOEC values were compared with a reviewed database containing the existing ecotoxicological data from saltwater organisms.

Performance assessment of AS-SBR and UF-MBR for hotel wastewater treatment.

A large number of tourist structures in Venice (Italy) have small sized on-site treatment systems for their wastewater. Due to its historical characteristics, the city has no public sewerage system and untreated hotel wastewater represents a serious hazard for its lagoon environment. This study focused on the wastewater facilities installed in two hotels adopting an Activated Sludge Sequencing Batch Reactor (AS-SBR) and an Ultra-Filtration Membrane Biological Reactor (UF-MBR). Their performance was checked in terms of both traditional physico-chemical and ecotoxicological parameters, the importance of which has recently been recognised by EU regulatory dispositions and OSPAR indications. Acute and sub-chronic endpoints were both considered on a whole effluent toxicity basis by means of Vibrio fischeri and Crassostrea gigas, respectively. The two months monitoring survey evidenced that the UF-MBR was more efficient than the AS-SBR in providing high-quality discharges under both chemical and ecotoxicological viewpoints.

Influence of storage methods, refrigeration or freezing, on the toxicity of wastewater samples to oyster embryos.

One of the main concerns in wastewater whole effluent assessment is the sampling phase and the sample chain of custody before any toxicity evaluation. The major problem is related to establishing the correct method for sample storage in order to perform toxicity bioassays. The toxicity of some domestic and glass factory industrial wastewater samples stored both by refrigeration at 4 +/- 1 degrees C for no more than three days, and freezing at -18 +/- 1 degrees C for no more than one month was compared via the embryo larval development bioassay with the oyster Crassostrea gigas. The results showed no significant differences between the toxicities of refrigerated and frozen wastewater samples. The wastewater classification, according to a score based on four toxicity classes, showed that the preservation methods did not alter the toxicity classification of the samples. In particular, it was demonstrated that the samples considered as 'not acutely toxic' after refrigeration were also found to have this classification after freezing.