Comparison of plastic pollution between waters and sediments in four Po River tributaries (Northern Italy).

The monitoring of plastic contamination in freshwaters is still pioneering in comparison with marine environments, and few studies analyzed the distribution of these pollutants in both aqueous and bottom compartments of continental waters. Therefore, the aim of this study was the comparison of plastic pollution in both waters and sediments of four Po River tributaries (Ticino, Adda, Oglio and Mincio Rivers), which outflow from the main Italian sub-alpine Lakes, in order to establish the strengths and weaknesses of both matrices. The main results pointed out a heterogeneous plastic contamination, with the lowest values in Ticino (0.9 ± 0.5 plastics/m3 in waters and 6.8 ± 4.5 plastics/kg dry weight - d.w. - in sediments) and the highest in Mincio (62.9 ± 53.9 plastics/m3 in waters and 26.5 ± 13.3 plastics/kg d.w in sediments), highlighting a plastic amount in sediments four times higher than waters. Plastic pollution, mainly due to microplastics, was associated principally to a domestic input in both waters and sediments of Ticino and Adda Rivers, as well as in sediments of Oglio, while an industrial pollution was found in waters and sediments of Mincio and Oglio waters. Our data clearly highlighted as the monitoring of both matrices provide complementary information for a holistic risk assessment of these emerging contaminants in freshwaters: the aqueous matrix provides an instantaneous picture of contamination, while sediments the history of pollution.

Biomonitoring of human activities recovery following lockdown in a highly touristic Mediterranean Island using Mytilus galloprovincialis.

Coastal waters face significant anthropogenic stress, particularly from tourism, exacerbating pollution, especially in areas like touristic islands. Ischia, the largest island in the Gulf of Naples and part of the Regno di Nettuno Marine Protected Area, suffers from pollution due to tourism and maritime traffic. During the initial SARS-CoV-2 lockdown from March to June 2020, Ischia was isolated, providing a unique opportunity to study pollutant release and its impact on coastal ecosystems. Adult Mytilus galloprovincialis mussels were transplanted to three sites on the island for active biomonitoring. Accumulation of chemicals in tissues and biomarkers related to metabolism, detoxification, and oxidative stress were measured. Results indicated that pollutants from daily activities entered the sea, affecting filter feeders. Translocated organisms showed modulated metabolic functions and biochemical changes, highlighting coastal vulnerability and calling for conservation efforts.

Unveiling the multilevel impact of four water-soluble polymers on Daphnia magna: From proteome to behaviour (a case study).

The ubiquitous presence of water-soluble polymers (WSPs) in freshwater environments raises concerns regarding potential threats to aquatic organisms. This study investigated, for the first time, the effects of widely used WSPs -polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyacrylic acid (PAA), and polyethylene glycol (PEG)- using a multi-level approach in the freshwater biological model Daphnia magna. This integrated assessment employed a suite of biomarkers, evaluation of swimming behaviour, and proteomic analysis to investigate the effects of three environmentally relevant concentrations (0.001, 0.5, and 1 mg/L) of the tested WSPs from molecular to organismal levels, assessing both acute and chronic effects. Our findings reveal that exposure to different WSPs induces specific responses at each biological level, with PEG being the only WSP inducing lethal effects at 0.5 mg/L. At the physiological level, although all WSPs impacted both swimming performance and heart rate of D. magna specimens, PAA exhibited the greatest effects on the measured behavioural parameters. Furthermore, proteomic analyses demonstrated altered protein profiles following exposure to all WSPs, with PVA emerging as the most effective.

Assessment of behavioural effects of three water-soluble polymers in zebrafish embryos.

The water-soluble polymers (WSPs) are widely used in many industrial applications and are present in several commonly used products due to their physical-chemical characteristics: as their name indicates, despite being synthetic polymers, they are able to solubilize in water. Because of this peculiar property, both the qualitative-quantitative evaluation in aquatic ecosystems and their potential (eco)toxicological effects have been neglected until now. The aim of this study was to evaluate the possible effects of three of the most widely used WSPs as polyacrylic acid (PAA), polyethylene glycol (PEG) and polyvinyl pyrrolidone (PVP) on the swimming behaviour of zebrafish (Danio rerio) embryos after the exposure to different concentrations (0.001, 0.5, 1 mg/L). The exposure lasted from the eggs' collection up to 120 h post fertilization (hpf) also using three different light intensity (300 lx, 2200 lx, 4400 lx) to better evaluate any effects related to different gradients of light/dark transitions. In order to analyze individual behavioural changes in embryos, their swimming movements were tracked and a number of parameters for locomotion and directionality were quantified. The main results showed that all three WSPs resulted in significant (p ≤ 0.05) variations in different movement parameters, suggesting a possible toxicity scale: PVP > PEG â‰« PAA.

Can COVID-19 pandemic change plastic contamination? The Case study of seven watercourses in the metropolitan city of Milan (N. Italy).

The more or less extensive lockdowns, quarantines, smart working and the closure of numerous recreational or personal care activities due to the COVID-19 pandemic have not only heavily changed the habits and behaviors of all of us, but have also had consequences on the release of some types of pollutants. The aim of this study was to evaluate the possible changes due to the indirect effects of the pandemic in the contamination of plastic mixtures sampled in 9 sites of the main watercourses of the metropolitan city of Milan (N. Italy), which is one of the major industrialized and urbanized areas in Italy. To achieve this goal, we carried out two sampling campaigns, the first one carried out in November 2019, before the arrival of the SARS-CoV-2 virus in Italy, the second in November 2020, during a severe regional lockdown that coincided with other restrictions imposed at the national level. The main results showed a difference in contamination of plastics between the two samplings, not so much due to a quantitative variation, but certainly qualitative. We obtained non-homogeneous data with respect to changes in the number of plastics sampled in the different waterbodies, while it was evident that the plastics' contamination has shifted from a primary and industrial origin to one due to a secondary origin of the sampled plastics, linked especially to the fragmentation of common use objects, or deriving from synthetic garments.

A realistic approach for the assessment of plastic contamination and its ecotoxicological consequences: A case study in the metropolitan city of Milan (N. Italy).

The study of the contamination of plastic mixtures sampled in natural environments is currently focused on their qualitative and quantitative assessment, while the evaluation of their effects on organisms is normally performed by experiments carried out at exposure conditions (size, shape, polymers) often far from the environmental ones. To improve the ecological realism, the aim of this study was to collect different plastic mixtures in 9 sampling stations located in 7 watercourses within the metropolitan city of Milan, one of the most anthropized and industrialized European areas, to evaluate both their qualitative and quantitative characteristics and, at the same time, to assess their ecotoxicological effects by exposing for 7 days some specimens of the freshwater bivalve Dreissena polymorpha to the mixtures collected in the sampling sites. The plastic characterization was performed by a Fourier-Transform Infrared spectrometer coupled with an optical microscope (µFT-IR), after several stages aimed to sample cleaning, separation of plastics and visual sorting. The possible effects caused by the plastic mixtures were carried out by the measurements of a biomarker suite to evaluate many cellular and molecular endpoints in mussel tissues. The main results showed a widespread and heterogeneous contamination of plastics in the entire metropolitan area, with contamination peaks found above all in the only two rivers of natural origin (Olona River and Lambro River) where comparable or higher values were reached than plastic concentrations measured in several European rivers. Despite this worrying contamination, the ecotoxicological data obtained after the exposures to the plastic mixtures collected in the selected water bodies showed only a mild effect on oxidative stress and on the variation of some antioxidant enzymes.

Are "liquid plastics" a new environmental threat? The case of polyvinyl alcohol.

Despite the pollution induced by plastics become a well-known and documented problem, bringing many countries to adopt restrictions about their production, commercialization and use, the impact of another emerging category of synthetic polymers, represented by the Water-Soluble Polymers (WSPs), also known as "liquid plastics", is overlooked by scientific community. WSPs are produced in large quantities and used in a wide plethora of applications such as food packaging, pharmaceuticals and personal care products, cosmetics and detergents, with a consequent continuous release in the environment. The aim of this study was the investigation of the possible toxicity induced by polyvinyl alcohol (PVA), one of the main produced and used WSPs, on two freshwater model organisms, the crustacean Daphnia magna and the teleost Danio rerio (zebrafish). We evaluated the effects of solubilized standard PVA powder and PVA-based commercial bags for carp-fishing, at 3 different concentrations (1 µg/L, 0.5 mg/L and 1 mg/L), through the exposures for 14 days of D. magna (daphnids; age < 24 h) and for 5 days of zebrafish embryos (up to 120 h post fertilization - hpf). As acute effects we evaluated the immobilization/mortality of specimens, while for chronic toxicity we selected several endpoints with a high ecological relevance, as the behavioural alteration on swimming performance, in real-time readout, and the activity of monoamine oxidase (MAO), a neuro-enzyme with a potential implication in the organism movement. The results showed the lack of significant effects induced by the selected substances, at all tested concentrations and in both model organisms. However, considering the wide plethora of available WSPs, other investigations are needed to provide the initial knowledge of risk assessment of these compounds contained in some consumer products.

Characterization of plastics and their ecotoxicological effects in the Lambro River (N. Italy).

This study had the dual objective of both the qualitative and quantitative assessment of plastic mixtures sampled in 5 different sites located along the Lambro River (northern Italy), and the contemporarily determination of the ecotoxicological effects of the same mixtures sampled, through 21-day laboratory exposures of the freshwater bivalve Dreissena polymorpha. The monitoring survey was carried out by a Fourier Transform Infrared Microscope System, while the ecotoxicological assessment was performed by the mussel mortality, a biomarker suite and the proteomics. The main results of the monitoring have highlighted some critical points, related to the concentration of plastics detected at Milan and, especially at the southernmost sampling station, where a daily flow of more than 6 million plastic debris has been estimated, ending directly into the Po River, the main Italian river. The ecotoxicological analysis highlighted how the toxicity is not exclusively due to the plastic concentration, but that the different characteristics of the polymers probably become more important. Furthermore, we observed an extensive mortality of bivalves exposed to the sampled mixtures in the two southernmost sampling stations, while the battery of biomarkers and the results of proteomics have highlighted how the sampled plastic mixtures caused an imbalance in the redox state, already indicated as a classic effect due to plastic exposure, but also an impact on energy stock and on some fundamental cellular pathways always linked to energy metabolism.

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.

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.