Removal of Mn and As from drinking water by red mud and pyrolusite.

Due to limited economic resources, which impede access to specific advanced technologies, many developing countries are still facing the challenge of reducing human exposure to heavy metals, which is primarily associated with the consumption of water contaminated through the discharge of poorly treated wastewater. In wastewater treatment technology, adsorption is sometime preferred to other approaches because of its high efficiency, easy handling, availability of different substrates and cost effectiveness. Moreover, increasing emphasis has recently been given to the use of low-cost adsorbents (generally solid wastes) for the treatment of polluted water, with a resulting double benefit for the environment. In this paper, the use of red mud and pyrolusite has been investigated for the removal of As and Mn from drinking water. Adsorption equilibrium data have been examined through the application of constant temperature models (isotherms), while batch and dynamic tests have been used to clarify the effects of pH, initial metal ion concentration and temperature on the adsorption performance, aiming at identifying the best conditions for the treatment. The combined use of the two adsorbents allows exploiting their properties synergistically, maximizing efficacy and sustainability without affecting process design and costs. In particular, 'clean' water (i.e. water with heavy metals contents below law limits) has been obtained even after the passage of a volume of solution higher than 40 bed volumes, and considering initial unrealistically high concentrations for the metals.

Antioxidant Hydroxytyrosol-Based Polyacrylate with Antimicrobial and Antiadhesive Activity Versus Staphylococcus Epidermidis.

The accumulation of reactive oxygen species (ROS) in microbial biofilms has been recently recognized to play a role in promoting antibiotic resistance in biofilm-growing bacteria. ROS are also over-produced when a medical device is implanted and they can promote device susceptibility to infection or aseptic loosening. High levels of ROS seem also to be responsible for the establishment of chronic wounds.In this study, a novel antioxidant polyacrylate was synthesized and investigated in terms of antimicrobial and antibiofilm activity. The polymer possesses in side-chain hydroxytyrosol (HTy), that is a polyphenolic compound extracted from olive oil wastewaters.The obtained 60 nm in size polymer nanoparticles showed good scavenging and antibacterial activity versus a strain of Staphylococcus epidermidis. Microbial adherence assays evidenced that the hydroxytyrosol-containing polymer was able to significantly reduce bacterial adhesion compared to the control. These findings open novel perspective for a successful use of this antioxidant polymer for the prevention or treatment of biofilm-based infections as those related to medical devices or chronic wounds.

Fate of the biofilm chips overflowed from a wastewater treatment plant.

In February 2018 over 100 millions of polyethylene biofilm chips overflowed from a wastewater treatment plant located at Capaccio Paestum (Italy) and due to the Thyrrhenian Sea currents, in few days they invaded the coasts of Campania, Lazio and Tuscany. During the following months the diffusion involves all the coasts of the western Mediterranean, including Spain, France and Tunisia. Samples of chips were recovered mainly along the Latium coasts (Italy) during the last 6 years. Following the exposure of the biofilm chips to the environmental conditions, the effect of natural weathering on polyethylene have been studied. The following annual decreases were evaluated: thickness 9.5 µm, diameter 18.5 µm and weight 3.7 mg while the average value of the size of all recovered items (n = 60) are: thickness = 2.936 ± 0.0406 mm, diameter = 44.349 ± 0.1266 mm and weight = 1.1593 ± 0.0248 g. Considering the weight loss, it was calculated that the complete mineralization of the disks will occur in 310 years producing about 0.5 tons of microplastics per year. FTIR analysis was used to investigate the change of chemical structure of the polyethylene. The Carbonyl index (CI), Vinyl index (VI) and Hydroxyl normalized absorbance peak were used to evaluate the polymer degradation while Scanning Electron Microscopy (SEM) was used to characterize the surface of the polymer samples. It was observed that erosion/degradation increases with time spent in the environment, above all from the last two years. The static contact angle was always >90° confirming that the surface of the biofilm chip is hydrophilic. The Oxygen/Carbon ratio increase with time: 0.18 and 0.27 has been found for 2018 and 2023 disks respectively confirming the progressive oxidative process. From TGA analysis a slightly reduction of decomposition temperature has been evaluated.

First evidence of plastics in coypu (Myocastor coypus)'s platforms.

Platforms are structures built by coypus for various purposes, such as reproduction, resting, and thermoregulation. In a coastal wetland of central Italy, during a study aimed at investigating the characteristics of coypu's platforms, it was recorded, for the first time worldwide, the presence of plastic in these structures. Through a transect survey, we censused 83 platforms, among which three (3.61%) were found with presence of macro- and megaplastics (polystyrene, polypropylene, and low-density polyethylene in film form; polyester, polyamide, and expanded polystyrene in fragments). Through the FTIR spectra, it was possible to highlight the degradation of the polymeric materials. To stimulate possible in-depth investigations at the level of the food chain (e.g., coypu predators, including canids) in wet habitats, we discussed possible causes and implications of plastic presence in coypus' nest structures.

Microplastic in an apex predator: evidence from Barn owl (Tyto alba) pellets in two sites with different levels of anthropization.

Plastic pollution in terrestrial and freshwater environments and its accumulation along food chains has been poorly studied in birds. The Barn owl (Tyto alba) is an opportunistic and nocturnal apex predator feeding mostly on small mammals. In this note, we reported evidence of microplastics (MPs) contamination in Barn owl pellets collected, for the first time, in two sites with different levels of anthropization (low: natural landscape mosaic vs. high extensive croplands). The following polymers have been recorded: polyvinylchloride (PVC), polyethylene (PE), expanded polyester (EPS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyester (PL), viscose, and starch-based biopolymer. We found significant higher MPs frequency in the most anthropized site. Our results suggest that pellet' analysis may represent a cost-effective method for monitoring MP contamination along food chains in terrestrial ecosystems.

Design of a 3D Amino-Functionalized Rice Husk Ash Nano-Silica/Chitosan/Alginate Composite as Support for Laccase Immobilization.

Recycling of agro-industrial waste is one of the major issues addressed in recent years aimed at obtaining products with high added value as a future alternative to traditional ones in the per-spective of a bio-based and circular economy. One of the most produced wastes is rice husk and it is particularly interesting because it is very rich in silica, a material with a high intrinsic value. In the present study, a method to extract silica from rice husk ash (RHA) and to use it as a carrier for the immobilization of laccase from Trametes versicolor was developed. The obtained mesoporous nano-silica was characterized by X-ray diffraction (XRD), ATR-FTIR spectroscopy, Scanning Elec-tron Microscopy (SEM), and Energy Dispersive X-ray spectroscopy (EDS). A nano-silica purity of about 100% was found. Nano-silica was then introduced in a cross-linked chitosan/alginate scaffold to make it more easily recoverable after reuse. To favor laccase immobilization into the composite scaffold, functionalization of the nano-silica with (γ-aminopropyl) triethoxysilane (APTES) was performed. The APTES/RHA nano-silica/chitosan/alginate (ARCA) composite al-lowed to obtain under mild conditions (pH 7, room temperature, 1.5 h reaction time) a robust and easily reusable solid biocatalyst with 3.8 U/g of immobilized enzyme which maintained 50% of its activity after six reuses. The biocatalytic system, tested for syringic acid bioremediation, was able to totally oxidize the contaminant in 24 h.

Microbial colonization patterns and biodegradation of petrochemical and biodegradable plastics in lake waters: insights from a field experiment.

Introduction: Once dispersed in water, plastic materials become promptly colonized by biofilm-forming microorganisms, commonly known as plastisphere. Methods: By combining DNA sequencing and Confocal Laser Scanning Microscopy (CLSM), we investigated the plastisphere colonization patterns following exposure to natural lake waters (up to 77 days) of either petrochemical or biodegradable plastic materials (low density polyethylene - LDPE, polyethylene terephthalate - PET, polylactic acid - PLA, and the starch-based MaterBi® - Mb) in comparison to planktonic community composition. Chemical composition, water wettability, and morphology of plastic surfaces were evaluated, through Transform Infrared Spectroscopy (ATR-FTIR), Scanning Electron Microscopy (SEM), and static contact angle analysis, to assess the possible effects of microbial colonization and biodegradation activity. Results and Discussion: The phylogenetic composition of plastisphere and planktonic communities was notably different. Pioneering microbial colonisers, likely selected from lake waters, were found associated with all plastic materials, along with a core of more than 30 abundant bacterial families associated with all polymers. The different plastic materials, either derived from petrochemical hydrocarbons (i.e., LDPE and PET) or biodegradable (PLA and Mb), were used by opportunistic aquatic microorganisms as adhesion surfaces rather than carbon sources. The Mb-associated microorganisms (i.e. mostly members of the family Burkholderiaceae) were likely able to degrade the starch residues on the polymer surfaces, although the Mb matrix maintained its original chemical structure and morphology. Overall, our findings provide insights into the complex interactions between aquatic microorganisms and plastic materials found in lake waters, highlighting the importance of understanding the plastisphere dynamics to better manage the fate of plastic debris in the environment.

Polypropylene Recovery and Recycling from Mussel Nets.

Mussels represent about one-third of all aquaculture products sold in the European Union. Theoretically, mussel production should be an environmentally friendly and sustainable activity (0.252 kg CO2 eq. per 1 kg of mussel produced against over 20 kg CO2 eq. per 1 kg of beef produced) but the abandoned plastic "socks" on the seabed and along beaches represent a significant environmental problem. The recovery and recycling of those polymer materials represents the proper management of the waste issue due to mussel farming. This study was performed to investigate, for the first time, the roles of the chemical oxidation actions on the detachment (and destruction) of organic matter (biofilm in particular) from the surface of the polypropylene "socks" used in sea farms in order to recover the polymer material and recycle it. In the experiments, oxidation by H2O2 and HNO3 was performed on the studied samples. The effects of the particle size of the fragments, oxidant concentration, agitation time and ultrasound application were determined. FTIR spectra and tensile mechanical properties of the samples after treatment were measured and compared with the virgin polymer material. The biodiversity and structure of the plastic-associated biofilm was also determined before and after the oxidation process. Based on the results of the characterization of the recovered polymer material, a process scheme was designed. The application of the developed process could significantly reduce the environmental risk associated with used mussel socks. The One LIFE (the EU's funding instrument for the environment and climate action) Project was recently founded based on this research.

Anthropogenic particles in coypu (Myocastor coypus; Mammalia, Rodentia)' faeces: first evidence and considerations about their use as track for detecting microplastic pollution.

Anthropogenic plastic litter is widespread in all environments, with particular emphasis on aquatic habitats. Specifically, although freshwater mammals are important as they are at the top of food web, research mainly focus on marine animals, while only few studies have been carried out on freshwater mammals. The main gap is that microplastics (MP) are completely understudied in freshwater mammals. Here, we reported the first evidence of the presence of anthropogenic particles (including MP) in coypu (Myocastor coypus)' faeces. Coypu is a rodent mammal inhabiting rivers and wetland areas, and we discussed our preliminary data suggesting the use of these tracks as possible future bioindicator of MP pollution in wetlands and freshwaters. We collected 30 coypu's faeces in "Torre Flavia wetland" nature reserve. Then, in laboratory, faeces were digested in 30 ml hydrogen peroxide (30%) for a week a 20 °C and analysed under stereoscope. All the suspected found MP were isolated in a petri dish, using FT-IR analysis to confirm the polymers. Overall, we recorded 444 natural and anthropogenic particles with most of items being fibres. FT-IR analysis of the 10% of the particles recovered revealed that 72% of them was not MP (mainly, polyethylene, polyethylene terephthalate, and polyamide). Also, the number of anthropogenic particles is not correlated with the faecal weight. Given that alien species, such as coypu, are widespread species, our results might have a great importance as these species and MP in faecal tracks may be used as undirect proxy of environmental bioavailability of MP pollution.

Plastisphere in lake waters: Microbial diversity, biofilm structure, and potential implications for freshwater ecosystems.

Once dispersed in water, microplastic (MP) particles are rapidly colonised by aquatic microbes, which can adhere and grow onto solid surfaces in the form of biofilms. This study provides new insights on microbial diversity and biofilm structure of plastisphere in lake waters. By combining Fourier Confocal Laser Scanning Microscopy (CLSM), Transform Infrared Spectroscopy (FT-IR) and high-throughput DNA sequencing, we investigated the microbial colonization patterns on floating MPs and, for the first time, the occurrence of eukaryotic core members and their possible relations with biofilm-forming bacterial taxa within the plastisphere of four different lakes. Through PCR-based methods (qPCR, LAMP-PCR), we also evaluated the role of lake plastisphere as long-term dispersal vectors of potentially harmful organisms (including pathogens) and antibiotic resistance genes (ARGs) in freshwater ecosystems. Consistent variation patterns of the microbial community composition occurred between water and among the plastisphere samples of the different lakes. The eukaryotic core microbiome was mainly composed by typical freshwater biofilm colonizers, such as diatoms (Pennales, Bacillariophyceaea) and green algae (Chlorophyceae), which interact with eukaryotic and prokaryotic microbes of different trophic levels. Results also showed that MPs are suitable vectors of biofilm-forming opportunistic pathogens and a hotspot for horizontal gene transfer, likely facilitating antibiotic resistance spread in the environments.

Searching Nanoplastics: From Sampling to Sample Processing.

Nanoplastics (NPs) are considered emerging pollutants, namely unregulated contaminants whose toxic effect on humans and the environment has been demonstrated or suspected. They are the result of the physical fragmentation of the plastics that over time reach smaller dimensions (<100 nm). The issues related to the characterization and quantification of NPs in the environmental matrices are mainly related to the infinitepsimal size, to the fact that they are found in bulk, and to the different physico-chemical forms in which the same polymer can evolve over time by degradation. To deal with the study of a new class of pollutants it is necessary to assess the entire analytical method, carefully considering every single step (sampling, cleanup, qualitative, and quantitative analysis) starting from the validation method in the laboratory. This paper reviews the analytical method steps, focusing on the first ones, which the current literature often underestimates: laboratory tests, sampling, and sample processing; in fact, most errors and the quality of the analyses often depend on them. In addition, all newly introduced sample processing methods were examined.

Effect of Acid Leaching Pre-Treatment on Gold Extraction from Printed Circuit Boards of Spent Mobile Phones.

The effect of a preliminary acid leaching for the recovery of gold by thiourea from printed circuit boards (PCBs) of spent mobile phones, was investigated. Preliminary leaching is aimed to recover copper in the leachate that would compete with gold in the successive leaching of the residue with thiourea, thus preventing the formation of the gold-thiourea complex. Two hydrometallurgical routes were tested for the recovery of copper first, and gold after. The first one was based on a two-step leaching that utilizes sulfuric acid and hydrogen peroxide in the preliminary leaching and then thiourea for the recovery of gold in the successive leaching: A copper and gold recovery of 81% and 79% were obtained, respectively. In the second route, nitric acid was used: 100% of copper was recovered in the leachate and 85% of gold in the thiourea successive leaching. The main operative parameters, namely thiourea and ferric sulphate concentrations, leach time, liquid-solid ratio, and temperature were studied according to a factorial plan strategy. A flowsheet of the processes was proposed, and a mass balance of both routes was obtained. Finally, qualitative considerations on the technical and economic feasibility of the different routes were made.

Preliminary indoor evidences of microplastic effects on freshwater benthic macroinvertebrates.

Plastics are to date considered one of the main detrimental drivers for the health of aquatic ecosystems, both in marine and inland waters. Regarding the latter habitat, it seems surprising how the plastic effects on benthic invertebrates are neglected since macroinvertebrates have a long tradition in the water quality assessment activities. In this context, we propose timely indoor observations on the exposure of caddisfly Odontocerum albicorne and mayfly Ephemera danica to various microplastic polymers (ABS, PET, PP, PS, PVDF). Three different experimental designs were performed on caddisflies and mayflies by exposing their larvae to natural and microplastic substrates. Our findings highlighted how microplastics affected both caddisflies in rebuilding its own case (after having removed the natural one) and mayflies burrowing. Particularly, all caddisflies rebuilt cases using the microplastic polymers provided instead of natural items only. Moreover, we provide the first evidence that mayflies burrow mainly in microplastic substrates rather than in natural ones. Our research highlights that macroinvertebrate larvae would use naturally occurring microplastics and this could be of particular concern in freshwaters with high contamination by plastics. Indeed, larvae appear to not necessarily perceive microplastics as a direct stressor. Further studies ought to be conducted to understand the chronic perturbation on larvae fitness and for example, on drift behaviour. Also, further investigations are needed to understand the potentialities of using plastics by benthic macroinvertebrates.

Removal of polyethylene glycols from wastewater: A comparison of different approaches.

Physicochemical methods such as adsorption on activated carbon, oxidation with either ozone or Fenton reagent, and chemical precipitation (coagulation), were assessed for the removal of polyethylene glycol (PEG) from wastewater. This contaminant is rarely investigated due to its low toxicity, although its presence limits the use of large water resources. The experimental tests showed that adsorption on activated carbon is well approximated by a Langmuir isotherm, and influenced by contact time, PEG molecular weight, pH, temperature, and initial PEG concentration. Ozonation allowed fragmenting the polymeric chains but was unable to remove completely the PEG, while about 85% of the total organic carbon (TOC) was removed by Fenton oxidation reaction by using a ratio between H2O2 and FeII close to 4. Coagulation did not produce results worthy of note, most likely because the uncharged PEG molecule does not interact with the iron hydroxide flocs. However, when performed after the Fenton oxidation (i.e., by simply raising the pH to values > 8), it allowed a further reduction of the residual TOC, up to 96% of the total, in the best case. Based on the resources used by each process studied and in consideration of the effectiveness of each of them, a semi-quantitative comparison on the sustainability of the different approaches is proposed.

On Tailoring Co-Precipitation Synthesis to Maximize Production Yield of Nanocrystalline Wurtzite ZnS.

Pyroelectric materials can harvest energy from naturally occurring ambient temperature changes, as well as from artificial temperature changes, notably from industrial activity. Wurtzite- based materials have the advantage of being cheap, non-toxic, and offering excellent opto-electrical properties. Due to their non-centrosymmetric nature, all wurtzite crystals have both piezoelectric and pyroelectric properties. Nanocrystalline wurtzite ZnS, being a room temperature stable material, by contrast to its bulk counterpart, is interesting due to its still not well-explored potential in piezoelectric and pyroelectric energy harvesting. An easy synthesis method-a co-precipitation technique-was selected and successfully tailored for nanocrystalline wurtzite ZnS production. ZnS nanopowder with nanoparticles of 3 to 5 nm in size was synthesized in ethyl glycol under medium temperature conditions using ZnCl2 and thiourea as the sources of Zn and S, respectively. The purified and dried ZnS nanopowder was characterized by conventional methods (XRD, SEM, TEM, TG and FTIR). Finally, a constructed in-house pilot plant that is able to produce substantial amounts of wurtzite ZnS nanopowder in an environmentally friendly and cost-effective way is introduced and described.

Litter impacts on marine birds: The Mediterranean Northern gannet as case study.

Litter are ubiquitous and increasing in the coastal and marine environments. Entanglement with litter is one of the principal causes of mortality in seabirds, but the population-level consequences are unknown. Currently, all seabirds collect litter for nesting material. Northern Gannets are not the exception and there are several cases where elevated percentages of polymers are part of the life cycle of gannets, especially during breeding. This baseline paper presents an analysis of litter content and its related impacts on the two gannet nests located in South France (Carry-Le-Rouet) and Northwest Italy (Portovenere) from 2017 to 2019. 654 items from both gannet nests were collected with 277 items (42%) being of natural origin, while 377 items (58%) were litter. Most of the nesting material was nautical cordage, which appears to be used preferentially. A more restrictive litter management regulation must be adopted to reduce litter generation from fishing/aquaculture-related activities.

Preparation and Characterization of Chitosan-Coated Manganese-Ferrite Nanoparticles Conjugated with Laccase for Environmental Bioremediation.

Bioremediation with immobilized enzymes has several advantages, such as the enhancement of selectivity, activity, and stability of biocatalysts, as well as enzyme reusability. Laccase has proven to be a good candidate for the removal of a wide range of contaminants. In this study, naked or modified MnFe2O4 magnetic nanoparticles (MNPs) were used as supports for the immobilization of laccase from Trametes versicolor. To increase enzyme loading and stability, MNPs were coated with chitosan both after the MNP synthesis (MNPs-CS) and during their formation (MNPs-CSin situ). SEM analysis showed different sizes for the two coated systems, 20 nm and 10 nm for MNPs-CS and MNPs-CSin situ, respectively. After covalent immobilization of laccase by glutaraldehyde, the MNPs-CSin situ-lac and MNPs-CS-lac systems showed a good resistance to temperature denaturation and storage stability. The most promising system for use in repeated batches was MNPs-CSin situ-lac, which degraded about 80% of diclofenac compared to 70% of the free enzyme. The obtained results demonstrated that the MnFe2O4-CSin situ system could be an excellent candidate for the removal of contaminants.

Microplastic pollution in perch (Perca fluviatilis, Linnaeus 1758) from Italian south-alpine lakes.

Microplastic particles (MPs) contamination of aquatic environments has raised a growing concern in recent decades because of their numerous potential toxicological effects. Although fish are among the most studied aquatic organisms, reports on MPs ingestion in freshwater environments are still scarce. Thus, there is still much to study to understand the uptake mechanisms, their potential accumulation among the food webs and their ecotoxicological effects. Here, MPs presence in the digestive system of one of the most widespread and commercially exploited freshwater fish, the perch (Perca fluviatilis, Linnaeus 1758), was investigated in four different south-alpine lakes, to assess the extent of ingestion and evaluate its relation to the body health condition. A total of 80 perch specimen have been sampled from the Italian lakes Como, Garda, Maggiore and Orta. Microplastic particles occurred in 86% of the analysed specimens, with average values ranging from 1.24 ± 1.04 MPs fish-1 in L. Como to 5.59 ± 2.61 MPs fish-1 in L. Garda. The isolated particles were mainly fragments, except in L. Como where films were more abundant. The most common polymers were polyethylene, polyethylene terephthalate, polyamide, and polycarbonate, although a high degree of degradation was found in 43% of synthetic particles, not allowing their recognition up to a single polymer. Despite the high number of ingested MPs, fish health (evaluated by means of Fulton's body condition and hepatosomatic index) was not affected. Instead, fullness index showed an inverse linear relationship with the number of ingested particles, which suggests that also in perch MPs presence could interfere with feeding activity, as already described for other taxa.

Diversity and predicted inter- and intra-domain interactions in the Mediterranean Plastisphere.

This study investigated the biogeography, the presence and diversity of potentially harmful taxa harbored, and potential interactions between and within bacterial and eukaryotic domains of life on plastic debris in the Mediterranean. Using a combination of high-throughput DNA sequencing (HTS), Causal Network Analysis, and Scanning Electron Microscopy (SEM), we show regional differences and gradients in the Mediterranean microbial communities associated with marine litter, positive causal effects between microbes including between and within domains of life, and how these might impact the marine ecosystems surrounding them. Adjacent seas within the Mediterranean region showed a gradient in the microbial communities on plastic with non-overlapping endpoints (Adriatic and Ligurian Seas). The largest predicted inter-domain effects included positive effects of a novel red-algal Plastisphere member on its potential microbiome community. Freshwater and marine samples housed a diversity of fungi including some related to disease-causing microbes. Algal species related to those responsible for Harmful Blooms (HABs) were also observed on plastic pieces including members of genera not previously reported on Plastic Marine Debris (PMD).

Preparation and Characterization of TPP-Chitosan Crosslinked Scaffolds for Tissue Engineering.

Scaffolds are three-dimensional porous structures that must have specific requirements to be applied in tissue engineering. Therefore, the study of factors affecting scaffold performance is of great importance. In this work, the optimal conditions for cross-linking preformed chitosan (CS) scaffolds by the tripolyphosphate polyanion (TPP) were investigated. The effect on scaffold physico-chemical properties of different concentrations of chitosan (1 and 2% w/v) and tripolyphosphate (1 and 2% w/v) as well as of cross-linking reaction times (2, 4, or 8 h) were studied. It was evidenced that a low CS concentration favored the formation of three-dimensional porous structures with a good pore interconnection while the use of more severe conditions in the cross-linking reaction (high TPP concentration and crosslinking reaction time) led to scaffolds with a suitable pore homogeneity, thermal stability, swelling behavior, and mechanical properties, but having a low pore interconnectivity. Preliminary biocompatibility tests showed a good osteoblasts' viability when cultured on the scaffold obtained by CS 1%, TPP 1%, and an 8-h crosslinking time. These findings suggest how modulation of scaffold cross-linking conditions may permit to obtain chitosan scaffold with properly tuned morphological, mechanical and biological properties for application in the tissue regeneration field.