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Potentially toxic elements (PTEs) presence in marine sediments can significantly affect the environmental quality and negatively influence economy and recreational activities in related areas. Accordingly, contamination monitoring and control in the marine environment is a fundamental task. In this work, four PTEs behavior (i.e. As, Hg, Pb, and Zn) in sandy foreshore sediments (SFSs) was thoroughly investigated at different pH, redox potential and temperature conditions of the marine water. For all the tests, the released As was 2.7-6 times higher than its initial concentration in water. Nonetheless, final mass balances showed that preferential release in the liquid phase occurred for Pb and Hg (up to 10 % and 9.1 %, respectively). Moreover, final Zn and Hg content increase in SFSs labile fractions indicated their higher bioavailability after the tests. The obtained results outline an approach useful to predict the contaminants behavior in marine matrices and support environmental monitoring and preservation strategies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

This study proposes the phytoremediation of a pyrene (PYR)-contaminated soil by Cannabis sativa L. The experimental campaign was conducted along a 60 days period using three different initial PYR concentrations (i.e., 50, 100 and 150 mg kg TS -1 of soil) in 300 mL volume pots under greenhouse conditions (18-25 °C and 45-55% humidity). After 60 days of hemp growth and flourishing, the highest PYR removal reached approximately 95% in planted soil, 35% higher than in the unplanted control. PYR accumulation was observed in both roots and aerial parts of the plant, with a higher PYR uptake at increasing initial PYR concentrations in soil. The initial PYR concentration affected the growth and, thus, the phytoremediation potential of C. sativa L., which was the result of different removal mechanisms. Overall, the lowest initial PYR concentration was the one that resulted in the highest PYR removal. The interaction between the plant roots and microorganisms in rhizosphere was likely associated with PYR removal in this study. The highest DHO activity of 66.26 μg INTF g -1 TS -1 was observed in the soil spiked with 50 mg PYR·kg TS -1 ., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Soil contamination by pyrene has increased over the years due to human-related activities, urgently demanding for remediation approaches to ensure human and environment safety. Within this frame, phytoremediation has been successfully applied over the years due to its green and cost-effectiveness features. The scope of this review includes the main phytoremediation mechanisms correlated with the removal of pyrene from contaminated soils and sediments to highlight the impact of different parameters and the supplement of additives on the efficiency of the treatment. Soil organic matter (SOM), plant species, aging time, environmental parameters (pH, soil oxygenation, and temperature) and bioavailability are among the main parameters affecting pyrene removal through phytoremediation. Phytoextraction only accounts for a small part of the entire phytoremediation process, but the addition of surfactants and chelating agents in planted soils could increase pyrene accumulation in plant tissues by 20% as a consequence of the increased pyrene bioavailability. Rhizodegradation is the main phytoremediation mechanism involved due to the activity of bacteria capable of degrading pyrene in the root area. Inoculated-planted soil treatments have the potential to decrease pyrene accumulation in shoots and roots by approximately 30 and 40%, respectively, further stimulating the proliferation of pyrene-degrading bacteria in the rhizosphere. Plant-fungi symbiotic association results in an enhanced accumulation of pyrene in shoots and roots of plants as well as a higher biodegradation. Finally, pyrene removal from soil can be improved in the presence of amendments, such as natural non-ionic surfactants, biochar, and bacterial mixtures., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

This paper proposes an innovative bioaugmentation approach for the remediation of polycyclic aromatic hydrocarbon (PAH) contaminated soils, based on a novel habitat-based strategy. This approach was tested using two inocula (i-24 and i-96) previously enriched through an anaerobic digestion process on wheat straw. It relies on the application of allochthonous microorganisms characterized by specific functional roles obtained by mimicking a natural hydrolytic environment such as the rumen. The inocula efficiency was tested in presence of naphthalene alone, benzo[a]pyrene alone, and a mix of both of them. In single-contamination tests, i-24 inoculum showed the highest biodegradation rates (84.7% for naphthalene and 51.7% for benzo[a]pyrene). These values were almost 1.2 times higher than those obtained for both contaminants with i-96 inoculum and in the control test in presence of naphthalene alone, while they were 3 times higher compared to the control test in presence of benzo[a]pyrene alone. In mixed-contamination tests, i-96 inoculum showed final biodegradation efficiencies for naphthalene and benzo[a]pyrene between 1.1 and 1.5 higher than i-24 inoculum or autochthonous biomass. Total microbial abundances increased in the bioaugmented tests in line with the PAH degradation. The microbial community structure showed the highest diversity at the end of the experiment in almost all cases. Values of the Firmicutes active fraction up to 7 times lower were observed in the i-24 bioaugmented tests compared to i-96 and control tests. This study highlights a successful bioaugmentation strategy with biological components that can be reused in multiple processes supporting an integrated and environmentally sustainable bioremediation system., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Natural organic matter (NOM) from Sphagnum peat soil is extracted in water and subjected to several investigations to obtain structural and conformational information. Data show that the extracted NOM is self-organized in colloidal aggregates of variable sizes (from nano to micro scales, depending on the solvent composition, i.e., ultrapure water, solutions with denaturing agents, acetone, ethanol). Aggregates are formed by highly heterogeneous classes of organic compounds. According to the results of nuclear magnetic resonance and fluorescence measurements, the three-dimensional structure of aggregates, revealed by scanning electron microscope imaging, is supposed to be stabilized by the exposition of polar functional groups to the solvent, with consequent formation of hydrogen bonds, dipole-interactions and cation bridging. In contrast, the inner part of the aggregates displays hydrophobic features and is hypothesized to be further reinforced by the establishment of π-stacking interactions. The structure is assumed to be a supramolecular aggregation of small-medium oligomeric fragments (Max 750 Da) in which priority pollutants are entrapped by dispersive forces. The structures are shown to be nanosized spheroidal particles further aggregated to form higher dimension supra-structures. Carbohydrates play primary role, stabilizing the structure and giving marked hydrophilic properties to the aggregates., (Copyright © 2021 Elsevier Inc. All rights reserved.)

This study proposes a comparison of different ex situ technologies aimed at the removal of polycyclic aromatic hydrocarbons from marine sediments in terms of performances, costs and energy balance. In accordance with the principles of water-energy nexus, anaerobic bioremediation, soil washing and thermal desorption were investigated under low liquid phase and temperature conditions using phenanthrene (PHE) as model compound. After 42 days of anaerobic bioremediation, the highest PHE biodegradation of 68 and 64% was observed under denitrifying and methanogenic conditions, respectively, accompanied by N 2 and CH 4 production and volatile fatty acid accumulation. During soil washing, more than 97% of PHE was removed after 60 min using a solid-to-liquid ratio of 1:3. Along the same treatment time, low-temperature thermal desorption (LTTD) allowed a PHE removal of 88% at 200 °C. The economic analysis indicated that LTTD resulted in a higher cost (i.e. 1782 € m -3 ) than bioremediation and soil washing (228 and 371 € m -3 , respectively). The energy balance also suggested that bioremediation and soil washing are more sustainable technologies as a lower required energy (i.e. 16 and 14 kWh m -3 , respectively) than LTTD (i.e. 417 kWh m -3 ) is needed.

The effect of different Na concentrations on the fate of trace metals (Cd, Cu, Ni, Zn) in standard OECD soil was evaluated by performing soil leaching column experiments. Five Na concentrations added in synthetic irrigation water (0, 1, 5, 10, 50 mM) were studied in order to evaluate the fate of the metals contained in both the irrigation water leachate and the soil layer. In all experiments, metals mostly accumulated on the top soil layer (0-0.5 cm), at variable concentrations according to the Na content in the artificial irrigation water. Nevertheless, concentration peaks of metal contamination occurred at different sampling time in the soil leachates depending on the metal and on influent water sodicity. Peaks of metals in the leachate appeared simultaneously with the release of organic matter and/or release of Al, suggesting significant involvement of colloids in metals transport. Sodium concentration (10-50 mM) was demonstrated to highly reduce colloidal mobilization leading to the accumulation of more than 95% of the influent metal in the top soil layer. Conversely, low Na concentrations (1-5 mM) favored colloidal transport leading to the recovery of metals in the soil leachates., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

This paper analyzes the effect of caesium (Cs) concentration on seed germination, seedling growth, root uptake, and leaf uptake of Lactuca sativa to understand the potential transfer of the metal from contaminated soil to humans through the food chain. The results of germination experiments show that seed germination and seedling growth strongly depend on increasing Cs concentration, with a decrease in the number of germinated seeds compared to the control up to 13.6% and a reduction in seedling growth up to 10.3% at the highest Cs tested concentration (15 mM). Uptake experiments indicate a low transfer of Cs from soil to leaves and roots of the plants, ranging between 0.06% and 2.2%. The transfer is found to be a not-monotone function of soil potassium (K) content, with highest values corresponding to 1-2 mM K 2 SO 4 . Increasing concentrations of K lead to lower translocation of Cs from roots to leaves. Values above the average amount applied (20 and 40 mM K 2 SO 4 ) almost stop the translocation, suggesting the use of a high amount of K 2 SO 4 protects the food chain from Cs contamination., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Seleniferous soil collected from the wheat ( L.)-grown agricultural land in Punjab, India, was characterized and the Se concentration in various soil fractions was determined by sequential extraction. The soil had a total Se content of 4.75 (±0.02) mg kg, of which 44% was observed in the oxidizable soil fraction. Soil flushing as an in situ technique was performed to simulate the Se migration pattern in case of rainfall or irrigation. Significant migration of Se from the upper layer to the lower layers was observed during water percolation through the soil column at a flow rate of 1 mL min, which could be attributed to Se reduction in the lower anoxic layers of the soil column. For ex situ treatment, the soil washing technique was optimized by varying different parameters such as treatment time, temperature, pH, liquid to solid (L:S) ratio, and presence of competing ions and oxidizing agents. Selenium extraction from soil was significantly improved by the presence of oxidizing agents in the washing solution: ∼38% Se was removed from the soil in the presence of 0.5% KMnO. In contrast, parameters such as treatment time, temperature, pH, L:S ratio, and competing ions did not significantly enhance the Se extraction efficiency. In this research, laboratory-scale in situ and ex situ treatment techniques for Se removal from soil were studied and optimized. The results provide an insight for large-scale Se removal and recovery from seleniferous soils., (Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.)

This paper presents the results of an experimental study aimed at investigating the effect of operative parameters on the efficiency of a soil flushing process, conducted on real contaminated soil containing high amounts of Cu and Zn. Soil flushing tests were carried out with Ethylenediamine- N , N '-disuccinic acid (EDDS) as a flushing agent due to its high biodegradability and environmentally friendly characteristics. Process parameters such as Empty-Bed Contact Time (EBCT) and EDDS solution molarity were varied from 21-33 h and from 0.36-3.6 mM, respectively. Effects on the mobility of cations such as Fe and Mn were also investigated. Results showed that very high performances can be obtained at [EDDS] = 3.6 mM and EBCT = 33 h. In these conditions, in fact, the amount of removed Cu was 53%, and the amount of removed Zn was 46%. Metal distribution at different depths from the top surface revealed that Cu has higher mobility than Zn. The process results were strongly dependent on the exchange of metals due to the different stability constants of the EDDS complexes. Finally, results from a comparative study showed that soil washing treatment reached the same removal efficiency of the flushing process in a shorter time but required a larger amount of the EDDS solution., Competing Interests: The authors declare no conflict of interest.

This paper presents an experimental study aimed at verifying the efficiency of a double-stage remediation process to be applied in former agricultural sites contaminated by illegal dumping of industrial wastes. The process, which includes an EDDS (Ethylenediamine-N,N'-disuccinic acid) enhanced washing, followed by a phytoremediation treatment, is applied at the lab scale for the remediation of a soil sampled in a territory known as Land of Fires (Italy) contaminated with Cu (∼400 mg kg -1 ) and Zn (∼250 mg kg -1 ). Phytoremediation is conducted using Lactuca sativa to verify, together with process efficiency, the potential risks due to metal accumulation in edible species. The results of the washing process show the possibility of removing the potential toxic metals from 44% to 77% for Cu and from 18% to 47% for Zn. The removal is well distributed among all soil fractions. There is almost no removal of other components which are fundamental for an agricultural soil. Results of the subsequent phytoremediation treatment indicate that both the contaminants and the residual EDDS/EDDS-chelates adsorbed into the soil generally negatively affect plant growth, reducing the number of germinated seeds up to 43%, and the shoot length up to 63%. Nonetheless, whenever the efficiency of the washing stage is high enough, no adverse effect is obtained on the plants. The efficiency of the phytoremediation stage mainly relies on leaf uptake, which accounts for up to 88% of the total removed Cu and up to 95% of the total removed Zn. Stabilization in the underground part of the plant is more contained because of the limited mass of the roots., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

This paper presents an innovative procedure for the recovery of SS-ethylenediamine-N,N'-disuccinic acid (EDDS) solution used for soil washing processes. The procedure is derived from that applied for the recovery of ethylenediamine-tetraacetic acid (EDTA), modifying and optimizing the choice of the chemical agents used for the protonation of the chelant, the exchange of the metals, and the final precipitation of the unwanted compounds. To select the reagents and test the proposed approach, an experimental study was conducted on real EDDS spent solutions, obtained washing a Cu and Zn real contaminated soil. According to the results obtained, the precipitation ranges from 30% to more than 90% for both Cu and Zn, depending on the adopted reagent sequence, and on the molar ratio between the salt and the chelant contained in the spent solution. Data were in agreement with chemical equilibrium predicted in ideal conditions. The recovered solutions had a reduced ability to remove the contaminants when applied in a new soil washing cycle (15% less for Cu and 30% less for Zn) because of the high concentration of alkaline metal ions required for the precipitation. At the same time, they were more biodegradable compared to non-treated solutions, confirming that EDDS-metal chelates may represent a threat for biological wastewater processes., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Contaminated soil has become a growing issue in recent years. The most common technique used to remove contaminants (such as metals) from the soil is the soil washing process. However, this process produces a final effluent containing chelating agents (i.e., ethylenediaminedisuccinic acid, also known as EDDS) and extracted metals (i.e., Cu, Fe, and Zn) at concentrations higher than discharge limits allowed by the Italian and Brazilian environmental law. Therefore, it is necessary to develop further treatments before its proper disposal or reuse. In the present study, soil washing tests were carried out through two sequential paths. Moreover, different artificial sunlight-driven photocatalytic treatments were used to remove Cu, Zn, Fe, and EDDS from soil washing effluents. Metal concentrations after the additional treatment were within the Brazilian and Italian regulatory limits for discharging in public sewers. The combined TiO 2 -photocatalytic processes applied were enough to decontaminate the effluents, allowing their reuse in soil washing treatment. Ecotoxicological assessment using different living organisms was carried out to assess the impact of the proposed two-step photocatalytic process on the effluent ecotoxicity. Graphical Abstract ᅟ.