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The management of digested sludge derived from treatment water plants is a problem worldwide due to the possible transfer of contamination from sludge to amended soil and, in turn, to humans. Within this work, through a chemometric experimental design, a robust GC-MS method for the simultaneous determination of two classes of micropollutants of concern (polycyclic aromatic hydrocarbons-PAHs-and polychlorinated biphenyls-PCBs-including dioxin-like compounds) was developed using microwave-assisted extraction (MAE). The method, which showed interesting greenness features in compliance with the 12 principles of Green Chemistry, allowed PCB and PAH extraction with recoveries higher than 75% (RSD < 14%) with method detection limits between 4.6 and 11.5 µg kg -1 (PAHs) and between 6.9 and 13.7 µg kg -1 (PCBs), without preconcentration. The matrix effect was below 20%. The validated protocol allowed the characterization of two digested sludges sampled in an urban and a peri-urban district, representative models of two scenarios of different anthropic impacts. This study highlighted higher contamination for the sludge derived from the urban area, accounted for by the 4-ring PAHs. In addition, since carcinogenic PAHs were detected, the environmental risk (by mean of the comparison of predicted vs predicted no-effect concentrations) and the carcinogenic human risk from dermal contact (through the calculation of the adsorbed lifetime average daily dose) were assessed in the case of soils amended with the sludges considered, pointing out that the measured concentrations do not pose a risk., (© 2024. The Author(s).)

Nine biochars were produced by co-pyrolysis of sawdust and biological sludge following the "design of experiment" approach. Two kinds of sludge (both deriving from the treatment of mixed industrial-municipal wastewater) and two types of woody waste were selected as categorical predicting variables, while contact time, pyrolysis temperature, and sludge percentage were used as quantitative variables. Biochars were analysed for their product characteristics and environmental compatibility based on the European Standards (EN 12915-1:2009) for materials intended for water treatment (i.e. ash content, water leachable polycyclic aromatic hydrocarbons (PAHs) and elements), as well as for specific surface area (SSA), using them as response variables of a multivariate partial least square multiple regression, whose results provided interesting insights on the relationships between pyrolysis conditions and biochar characteristics. Biochars produced with sludge and/or providing the highest SSA values (258-370 m 2  g -1 ) were selected to undergo a sustainable chemical treatment using a by-product of the gasification of woody biomass, complying in all cases with European Standards and achieving therefore the end-of-waste status for sewage sludge. The biochar deriving from the highest percentage of sludge (30% by weight) and with the highest SSA (390 m 2  g -1 ) was thermally activated achieving SSA of 460 m 2  g -1 and then tested for the sorption of direct yellow 50 and methylene blue in ultrapure water and real wastewater, compared to a commercial activated carbon (AC). The biochar showed Langmuir sorption maxima (Q m ) 2-9 times lower than AC, thus highlighting promising sorption performances. Q m for methylene blue in wastewater (28 mg‧g -1 ) was confirmed by column breakthrough experiments., (© 2024. The Author(s).)

The aim of the current work is to evaluate the effect of a mixture of olive mill wastewater (OMWW) and urban wastewater (UW) on constructed wetland (CW) substrate physicochemical parameters, and to study the abundance and behaviour of microbial community at different depths. In this regard, substrate samples were investigated at three depth levels (0-10 cm, 10-20 cm and 20-30 cm) inside a pilot scale CW treating the mixture. In order to compare the obtained results with the conventional case, a control (CW pilot plant treating only UW) was implemented. Result shows that an increase in electrical conductivity (from 0.134 to 0.222 mS/cm in 0-10 cm and from 0.131 to 0.283 mS/cm in 10-20 cm), total dissolved salts (from 65.45 to 108.67 mg/kg in 0-10cm and from 64.33 to 135.3 mg/kg in 10-20 cm), total organic carbon (from 0.86 to 6.84%), total nitrogen (from 0.1 mg/kg to 0.45, 0.43 and 0.41 mg/kg, in 0-10 cm, 10-20 cm and 20-30 cm respectively) and C/N ratio take place in the substrate after the treatment of the mixture. As for the microbiological parameters, treating the mixture in a CW results in an increase in the yeast and fungi which may optimize the biodegradation of compounds such as polyphenols that are non-easily degraded., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Among the numerous clean-up techniques for water treatment, sorption methods are widely used for the removal of trace metals. Phragmites australis is a macrophyte commonly used in constructed wetlands for water purification, and in the last decades, its use as biosorbent has attracted increasing attention. In view of a circularly economy approach, this study investigated improvement of trace metal removal by recycling the biomass of P. australis colonizing a constructed wetland, which operates as post-treatment of effluent wastewater from an activated sludge plant serving the textile industrial district of Prato (Italy). After the annual mowing of the reed plants, the biomass was dried and blended to derive a sustainable and eco-friendly biosorbent and its sorption capacity for Fe, Cu, and Zn was investigated comparing the batch system with the easier-to-handle column technique. The possibility of regeneration and reuse of the biosorbent was also evaluated. The biomaterial showed an interesting sorption capacity for Cu, Fe, and Zn, both in batch and in column experiments, especially for Fe ions. The immobilization of the biosorbent in column filters induced some improvement in the removal efficiency, and, in addition, this operation mode has the advantage of being much more suitable for practical applications than the batch process.

The presence of residual color in treated textile wastewater above the regulation limits is still a critical issue in many textile districts. Innovative, polymer-derived ceramics of the Si-C-O system were here synthesized in order to obtain porous nanocomposite materials where a free carbon phase is dispersed into a silicon carbide/silicon oxycarbide network. The sorbents were comprehensively characterized for the removal of two model water-soluble dyes (i.e., the cation methylene blue and the zwitterion rhodamine B). Adsorption is very rapid and controlled by intra-particle and/or film diffusion, depending on dye concentration. Among the nanocomposites studied, the SiOC aerogel (total capacity about 45 mg/g, is easily regenerated under mild treatment (250 °C, 2 h). Adsorption of dyes is not affected by the matrix composition: removals of 150 mg/L methylene blue from river water and simulated textile wastewater with high content of metal ions (2-50 mg/L) and chemical oxygen demand (800 mg/L) were higher than 92% and quantitative for a dye concentration of 1 mg/L.

This work investigated if the assessment of tolerance to trace metals can depend on plant density in the experimental design. A non-metallicolous and a metallicolous populations of Silene paradoxa were hydroponically cultivated at increasing density and in both the absence (-Cu conditions) and excess of copper (+Cu conditions). In -Cu conditions, the metallicolous population showed a lower susceptibility to plant density in comparison to the non-metallicolous one, explained by a higher capacity of the metallicolous population to exploit resources. In +Cu conditions, an alleviating effect of increasing density was found in roots. Such effect was present to a greater extent in the non-metallicolous population, thus making the populations equally copper-tolerant at the highest density used. In shoots, an additive effect of increasing plant density to copper toxicity was reported. Its higher intensity in the metallicolous population reverted the copper tolerance relationship at the highest plant densities used. In both populations, a density-induced decrease in root copper accumulation was observed, thus concurring to the reported mitigation in +Cu conditions. Our work revealed the importance of density studies on the optimization of eco-toxicological bioassays and of metal tolerance assessment and it can be considered the first example of an alleviating effect of increasing plant number on copper stress in a metallophyte.

Glyphosate is a worldwide-used herbicide occurring in many monitoring campaigns. Efficient technologies are currently unavailable for glyphosate removal from waters. In this work, a SBA-15 mesoporous silica-based material (Fe-NH 2 -SBA-15) was synthesized and studied for the adsorption of glyphosate from waters. In order to promote specific interactions between the sorbent and glyphosate via phosphoric group, iron oxide nanoparticles were encapsulated and a surface functionalization with (3-aminopropyl)triethoxysilane was accomplished. The adsorption of glyphosate on Fe-NH 2 -SBA-15 was investigated as a function of (i) pH, (ii) ionic strength (I), and (iii) adsorbate to adsorbent ratio (C), using a two-level, three-factor experimental design. The experimental design allowed for understanding the effect of the abovementioned variables and for proposing experimental conditions for quantitative removal (pH = 2.1, I = 1⋅10 -2  M and C = 0.35) under both batch and dynamic conditions. Interaction mechanism between glyphosate and Fe-NH 2 -SBA-15 sorbent was elucidated by studying the adsorption behavior of sorbents derived from the intermediate stages of synthesis and by desorption tests. Fe-NH 2 -SBA-15 sorbent can be quantitatively regenerated by 12.5 mM NaOH, and can be reused at least for five adsorption/desorption cycles. Quantitative removal of glyphosate from inlet and effluent wastewaters from a wastewater treatment plant is shown.

Within the last few years, the presence of bentazone herbicide has been observed in many water resources. For the first time, removal of bentazone using mesoporous silica was investigated revealing reversible adsorption. The adsorption isotherm was well described using the Freundlich model. The affinity towards bentazone is strongly affected by pH in the range of 2-7, decreasing with the increase of the pH, becoming negligible at the neutrality. Regeneration of the adsorbent was possible, and a recovery as high as 70 % was obtained using CH3OH-NaOH solution. Furthermore, appreciable recovery (47 %) was also obtained using water. Applications on the purification of lake water and wastewaters, both characterized by a significant organic carbon load, spiked with 2 mg L(-1) bentazone were tested, observing removal yields in the range of 61-73 %. Taking advantage of the fast adsorption kinetics observed, an in-flow purification treatment was set-up, with quantitative removal of bentazone from polluted water.

This work was planned for providing useful information about the use of excluder metallophytes for phytostabilization of soils contaminated also with elements scarcely represented in the metalliferous environment of origin. To this aim, we investigated tolerance and accumulation of several different elements in a metallicolous and a nonmetallicolous population of Silene paradoxa through a hydroponic experiment. S. paradoxa metallicolous population showed increased tolerance not only to all the metals highly represented in the environment of origin but also to some of those scarcely present. Therefore, our results deposed in favor of the occurrence of the co-tolerance phenomenon in S. paradoxa for some elements. Metal accumulation was higher in the roots than in the shoots and lower in the metallicolous population than in the nonmetallicolous one, thus showing tolerance mechanisms to be based largely on metal exclusion. Anyway, the relative contribution of avoidance and of internal tolerance to metal tolerance was shown to be element-dependent. Present data revealed that metallicolous plants can effectively posses metal co-tolerances, which deserve to be investigated; as such, plants can actually represent a precious and exploitable tool also for the phytostabilization of soils contaminated with elements underrepresented in the environment of their origin.