Publications by authors named "Marco Race"

27 Publications

  • Page 1 of 1

Long-term multi-endpoint exposure of the microalga Raphidocelis subcapitata to lanthanum and cerium.

Sci Total Environ 2021 Oct 2;790:148229. Epub 2021 Jun 2.

Department of Biology, University of Naples Federico II, Complesso Universitario di Monte Sant'Angelo, Via Cinthia 26, 80126 Naples, Italy. Electronic address:

Significant release of rare earth elements (REEs) into the environment is mainly due to active or abandoned mining sites, but their presence is globally increasing due to their use in several industrial sectors. The effects on primary producers as Raphidocelis subcapitata are still limited. This research focused on La and Ce as the two most widespread REEs that can be currently found up to hundreds of μg/L in water and wastewater. Microalgae were exposed to La and Ce for 3 days (pH = 7.8) (short-term exposure) to derive the effective concentrations inhibiting the growth on 10% (EC10) of the exposed population. EC10 values (0.5 mg/L of La and 0.4 mg/L of Ce) were used for the 28 days long-term exposure (renewal test) to observe after 7, 14, 21, and 28 days on a multi-endpoint basis microalgae growth inhibition (GI), biomarkers of stress (reactive oxygen species (ROS), superoxide dismutase (SOD), and catalase (CAT)), and bioconcentration. Results evidenced that La and Ce EC10 increased GI (day 28) up to 38% and 28%, respectively. ROS, CAT, and SOD activities showed differential responses from day 7 to day 14, 21, and 28, suggesting, in most of the cases, that La and Ce effects were counteracted (i.e., being the values at day 28 not significantly different, p > 0.05, from the relative negative controls), except for La-related ROS activities. La and Ce significantly bioconcentrated in microalgae populations up to 2- and 5-fold (i.e., at day 28 compared to day 7), in that order. Bioconcentrated La and Ce were up to 3157 and 1232 μg/g dry weight (day 28), respectively. These results suggested that low La and Ce concentrations can be slightly toxic to R. subcapitata having the potential to be bioaccumulated and potentially transferred along the food web.
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http://dx.doi.org/10.1016/j.scitotenv.2021.148229DOI Listing
October 2021

Feasibility study of saffron cultivation using a semi-saline water by managing planting date, a new statement.

Environ Res 2021 Aug 8;203:111853. Epub 2021 Aug 8.

Department of Civil and Mechanical Engineering, University of Cassino and Southern Lazio, Cassino, 03043, Italy. Electronic address:

In the current study the possibility of saffron (Crocus sativus L.) cultivating using semi-saline water was investigated at different planting dates. The salinity of irrigation water and soil were 2.9 and 5.8 dS m, respectively. The results showed that saffron had an acceptable potential for cultivation using semi-saline water in saline soils. The early planting dates went through the developmental stages faster, meaning saffron corms sown in early October sprouted earlier, flowers appeared faster and fully flowering occurred earlier. Nevertheless, plant senescence was the same in all planting dates. The highest percentage of corms sprouting and flowering were obtained in the early October planting dates in both years, which were matched with canopy temperature distribution. The highest flowers weight as well as stigma fresh and dry weight were obtained on the 13 October planting date within the 3 years study reaching the maximum values during the third year. Electrolyte leakage was higher in the last planting date, while photosynthesis pigments were more in early to mid-October planting dates. These effects might be related to damage of freezing temperature to physiological processes. Shoot dry weight and water productivity were the highest in early October planting dates. The shoot biomass on October 13 planting date was enough to be considered as a new forage source in semi-saline conditions. It seems that cultivation of saffron with semi-saline water is possible by considering a proper planting date, adequate leaching requirement and accurate irrigation management.
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http://dx.doi.org/10.1016/j.envres.2021.111853DOI Listing
August 2021

Characterization of anthropogenic organic matter and its interaction with direct yellow 27 in wastewater: Experimental results and perspectives of resource recovery.

Chemosphere 2021 Jul 11;286(Pt 1):131528. Epub 2021 Jul 11.

College of Architecture and Environment, Sichuan University, Chengdu, 610065, China. Electronic address:

The concept of natural organic matter of anthropogenic origin is introduced and its characteristics and interaction with chemical pollutants are investigated by adopting several distinct analytic methodologies. Scanning electron microscopy indicates that the used sample of anthropogenic organic matter (AOM) has an amphiphilic nature, which allows its supramolecular organization in water. Fourier transform infrared spectroscopy, in turn, gives a clear indication about the presence of polysaccharide markers, lipidic and amidic fractions, and suggests the absence of free organic acid. AOM sample and AOM mixed with dye sample were examined by the three-dimensional excitation-emission matrix fluorescence spectra and the nuclear magnetic resonance mono-dimensional spectra. The results highlighted the interactions occurring between the AOM and the reactive dye, selected as a representative chemical pollutant. Electron Spin Resonance confirms that the used AOM is able to completely include the dye in its structure. Overall, the obtained results indicate that the fate, transport, and toxicity of pollutants in the environment can be drastically influenced by the presence of AOM.
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http://dx.doi.org/10.1016/j.chemosphere.2021.131528DOI Listing
July 2021

Phenanthrene biodegradation in a fed-batch reactor treating a spent sediment washing solution: Techno-economic implications for the recovery of ethanol as extracting agent.

Chemosphere 2021 Jul 7;286(Pt 1):131361. Epub 2021 Jul 7.

Department of Civil, Architectural and Environmental Engineering, University of Napoli Federico II, Via Claudio 21, 80125, Napoli, Italy.

The continuous dredging of sediments contaminated by polycyclic aromatic hydrocarbons such as phenanthrene (PHE) has required the employment of high-efficiency technologies, including sediment washing (SW). However, the large amount of generated spent SW effluents requires the development of effective, eco-friendly and cost-saving approaches, which can tackle the waste formation in favor of the recovery of chemicals. This study proposes the treatment of a spent SW solution containing ethanol (EtOH) as extracting agent, by testing different initial PHE concentrations (i.e. 20-140 mg L) within six consecutive cycles in a fed-batch bioreactor under aerobic conditions. The biological process achieved a PHE removal of 63-91% after the enrichment of PHE-degrading bacteria and the proper supplementation of nutrients, and was mainly affected by the initial PHE concentration value and the excessive decrease of pH and dissolved oxygen. Achromobacter, Sphingobacterium and Dysgonomonas genera were mainly involved in PHE degradation, which followed a first-order kinetic model (R = 0.652-0.928) with a degradation rate and half-life time of 0.127-1.177 d and 0.589-2.912 d, respectively. A techno-economic assessment revealed that a virtuous operation of SW, EtOH recovery and biodegradation of the SW solution can allow the recovery of up to 1.35 tons of EtOH per ton of remediated sediment and the decrease of the overall costs by 50%.
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http://dx.doi.org/10.1016/j.chemosphere.2021.131361DOI Listing
July 2021

New research on reduction and/or elimination of hazardous substances in the design, manufacture and application of chemical products.

Environ Res 2021 Jun 25;201:111601. Epub 2021 Jun 25.

Laboratory of Toxicology and Environmental Health, School of Medicine, IISPV, Universitat Rovira I Virgili, Reus, Spain.

The Virtual Special Issue (VSI) "New research on reduction and/or elimination of hazardous substances in the design, manufacture and application of chemical products" was initially associated to the "International Conference on Green Chemistry and Sustainable Engineering, GreenChem-20" that was postponed due to the COVID-19 pandemic. Anyway, the international conference will take place in the near future. However, the VSI was maintained in this journal, received a high number of submissions, and selected manuscripts have been accepted after peer-reviewing. The published papers constitute a set of high-quality contributions, which, in the future, could be complemented with others related to additional conferences about similar topics. In this editorial piece, the Editors include brief comments on papers accepted for publication in the Special Issue, as well as additional aspects of interest related to the subject.
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http://dx.doi.org/10.1016/j.envres.2021.111601DOI Listing
June 2021

New research on water, waste and energy management, with special focus on antibiotics and priority pollutants.

Environ Res 2021 Jun 24;201:111582. Epub 2021 Jun 24.

Laboratory of Toxicology and Environmental Health, School of Medicine, IISPV, Universitat Rovira I Virgili, Reus, Spain.

The Editors of the Virtual Special Issue (VSI) "New Research on Water, Waste and Energy Management, with Special Focus on Antibiotics and Priority Pollutants" (VSI WWEM-20) here present details corresponding to papers that have been accepted, as well as further comments on the matter. It should be noted that the VSI should be associated to a Conference that had been initially programmed to be held in Rome during the summer of 2020, Unfortunately, it was postponed due to the COVID-19 pandemic. That conference was one of those within the series called "International Congress on Water, Waste and Energy Management". Although the Conference was postponed, the Call for Papers for the VSI was maintained by this journal. As a result, a set of very interesting papers were accepted after a careful peer-review process. We hope that it will be complemented with additional VSIs associated to future conferences corresponding to the series, increasing the knowledge on the topic.
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http://dx.doi.org/10.1016/j.envres.2021.111582DOI Listing
June 2021

Phytoremediation of pyrene-contaminated soils: A critical review of the key factors affecting the fate of pyrene.

J Environ Manage 2021 Sep 27;293:112805. Epub 2021 May 27.

Department of Civil, Architectural and Environmental Engineering, University of Napoli Federico II, Via Claudio 21, 80125, Napoli, Italy.

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.
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http://dx.doi.org/10.1016/j.jenvman.2021.112805DOI Listing
September 2021

Bioaugmentation strategy to enhance polycyclic aromatic hydrocarbons anaerobic biodegradation in contaminated soils.

Chemosphere 2021 Jul 23;275:130091. Epub 2021 Feb 23.

Department of Civil, Architectural and Environmental Engineering, University of Naples "Federico II", Via Claudio 21, 80125, Naples, Italy.

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.
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http://dx.doi.org/10.1016/j.chemosphere.2021.130091DOI Listing
July 2021

SARS-CoV-2 and other viruses in soil: An environmental outlook.

Environ Res 2021 07 7;198:111297. Epub 2021 May 7.

Department of Civil and Mechanical Engineering, University of Cassino and Southern Lazio, Via Di Biasio 43, 03043, Cassino, Italy. Electronic address:

In the present review, the authors shed light on the SARS-CoV-2 impact, persistence, and monitoring in the soil environment. With this purpose, several aspects have been deepened: i) viruses in soil ecosystems; ii) direct and indirect impact on the soil before and after the pandemic, and iii) methods for quantification of viruses and SARS-CoV-2 monitoring in soil. Viruses are present in soil (i.e. up to 417 × 10 viruses per g TS in wetlands) and can affect the behavior and ecology of other life forms (e.g. bacteria), which are remarkably important for maintaining environmental equilibrium. Also, SARS-CoV-2 can be found in soil (i.e. up to 550 copies·g). Considering that the SARS-CoV-2 is very recent, poor knowledge is available in the literature on persistence in the soil and reference has been made to coronaviruses and other families of viruses. For instance, the survival of enveloped viruses (e.g. SARS-CoV) can reach 90 days in soils with 10% of moisture content at ambient. In such a context, the possible spread of the SARS-CoV-2 in the soil was evaluated by analyzing the possible contamination routes.
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http://dx.doi.org/10.1016/j.envres.2021.111297DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC8102436PMC
July 2021

Haloculture: A system to mitigate the negative impacts of pandemics on the environment, society and economy, emphasizing COVID-19.

Environ Res 2021 07 8;198:111228. Epub 2021 May 8.

Pakistan Academy of Sciences, Islamabad, Pakistan.

COVID-19 (coronavirus disease) is a global pandemic that started in China in 2019 and has negatively affected all economic sectors of the world, including agriculture. However, according to estimates in different countries, agriculture has suffered less than other sectors such as construction, industry and tourism, so agricultural development can be a good option to compensate for the economic damage caused to other sectors. The quality of available water and soil resources for agricultural development is not only limited, but is also decreasing incrementally, so the use of saline and unconventional soil and water resources is inevitable. Biosaline agriculture or haloculture is a system in which highly saline water and soil resources are used sustainably for the economic production of agricultural crops. It seems that in the current situation of the world (with COVID-19's impact on agriculture on the one hand and the quantitative and qualitative decline of freshwater and soil on the other), haloculture with a re-reading of territorial capabilities has good potential to provide a part of human food supply. In this review article, the potential of haloculture to offset the adverse impacts of the pandemic is analyzed from five perspectives: increasing the area under cultivation, using unconventional water, stabilizing dust centers, increasing the body's immune resistance, and reducing losses in agribusiness due to the coronavirus. Overall, haloculture is an essential system, which COVID-19 has accelerated in the agricultural sector.
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http://dx.doi.org/10.1016/j.envres.2021.111228DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC8110177PMC
July 2021

Supramolecular aggregation of colloidal natural organic matter masks priority pollutants released in water from peat soil.

Environ Res 2021 04 29;195:110761. Epub 2021 Jan 29.

Department of Civil, Architectural and Environmental Engineering (DICEA), University of Naples Federico II, Via Claudio 21, 80125, Naples, Italy; BAT Center - Interuniversity Center for Studies on Bioinspired Agro-Environmental Technology, University of Napoli "Federico II", Portici (NA), Italy.

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.
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http://dx.doi.org/10.1016/j.envres.2021.110761DOI Listing
April 2021

The addition of biochar as a sustainable strategy for the remediation of PAH-contaminated sediments.

Chemosphere 2021 Jan 7;263:128274. Epub 2020 Sep 7.

Department of Civil, Architectural and Environmental Engineering, University of Napoli Federico II, Via Claudio 21, 80125, Napoli, Italy.

The contamination of sediments by polycyclic aromatic hydrocarbons (PAHs) has been widely spread for years due to human activities, imposing the research and development of effective remediation technologies for achieving efficient treatment and reuse of sediments. In this context, the amendment of biochar in PAH-contaminated sediments has been lately proposed as an innovative and sustainable technology. This review provides detailed information about the mechanisms and impacts associated with the supplementation of biochar to sediments polluted by PAHs. The properties of biochar employed in these applications have been thoroughly examined. Sorption onto biochar is the main mechanism involved in PAH removal from sediments. Sorption efficiency can be significantly improved even in the presence of a low remediation time (i.e. 30 d) when a multi-PAH system is used and biochar is provided with a high dosage (i.e. by 5% in a mass ratio with the sediment) and a specific surface area of approximately 360 m g. The use of biochar results in a decrease (i.e. up to 20%) of the PAH degradation during bioaugmentation and phytoremediation of sediments, as a consequence of the reduction of PAH bioavailability and an increase of water and nutrient retention. In contrast, PAH degradation has been reported to increase up to 54% when nitrate is used as electron acceptor in low-temperature biochar-amended sediments. Finally, biochar is effective in co-application with Fe for the persulfate degradation of PAHs (i.e. up to 80%), mainly when a high catalyst dose and an acidic pH are used.
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http://dx.doi.org/10.1016/j.chemosphere.2020.128274DOI Listing
January 2021

Novel Bioderived Composites from Wastes.

Materials (Basel) 2020 Jun 5;13(11). Epub 2020 Jun 5.

Department of Civil, Environmental, Land, Building Engineering and Chemistry, Polytechnic University of Bari, via E. Orabona, 4, 70125 Bari, Italy.

The recycling and reuse of solid wastes can be considered important challenges for civil and environmental applications in the frame of a more sustainable model of development and the consumption of new resources and energy [...].
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http://dx.doi.org/10.3390/ma13112571DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7321454PMC
June 2020

Comparing performances, costs and energy balance of ex situ remediation processes for PAH-contaminated marine sediments.

Environ Sci Pollut Res Int 2020 Jun 24;27(16):19363-19374. Epub 2020 Mar 24.

Department of Civil, Architectural and Environmental Engineering, University of Napoli Federico II, Via Claudio 21, 80125, Napoli, Italy.

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 and CH 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) than bioremediation and soil washing (228 and 371 € m, 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, respectively) than LTTD (i.e. 417 kWh m) is needed.
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http://dx.doi.org/10.1007/s11356-020-08379-yDOI Listing
June 2020

Data of OECD soil and leachate resulting from irrigation with aqueous solution containing trace metals at increasing sodium concentration.

Data Brief 2019 Aug 17;25:104276. Epub 2019 Jul 17.

Department of Civil, Architectural and Environmental Engineering, University of Naples Federico II, Via Claudio 21, 80125 Naples, Italy.

The accumulation of trace metals in soils is one of the main drawbacks when reclaimed waters are used as irrigation sources in agriculture. Such secondary water sources often also contain high levels of salinity and in detail sodium. How the presence of sodium influences the fate of trace metals in the environment is still obscure and of primary importance in defining sustainable agricultural management guidelines. Standard OECD soil columns were subjected to 25 days irrigation with aqueous solutions containing trace concentrations of Cd, Cu, Ni and Zn at increasing sodium content. The dataset is supplementary to the data presented and discussed in "Effect of sodium concentration on mobilization and fate of trace metals in standard OECD soil" [1]. The leachates collected from the columns were deeply characterized in terms of concentration of metals, organic (monitored through UV-VIS, 3DEEM, E/E ratio, COD) and inorganic matter (monitored as Al concentration). The dataset was analyzed by PCA and "Paerson" correlation coefficient.
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http://dx.doi.org/10.1016/j.dib.2019.104276DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6690663PMC
August 2019

A simplified model to simulate bioaugmented anaerobic digestion of lignocellulosic biomass: Biogas production efficiency related to microbiological data.

Sci Total Environ 2019 Nov 4;691:885-895. Epub 2019 Jul 4.

Department of Civil, Architectural and Environmental Engineering, University of Naples "Federico II", Via Claudio 21, 80125 Naples, Italy.

Mathematical model applications for the bioaugmented anaerobic digestion (BAD) process seem to be lacking in the scientific literature, even more so when related to microbiological data. The present study suggests a simplified mathematical model to investigate and simulate the process kinetics of bioaugmented anaerobic digestion (BAD) aimed at improving biogas production from wheat straw (WS). Bioaugmented conditions were obtained through a mixed inoculum of anaerobic ruminal fungi (ARF) and hydrogen-producing fermenting bacteria (F210) added to a methanogenic inoculum. The investigation focused on two process configurations characterized by a mono (I-BAD) and two-stage (II-BAD) process and a conventional anaerobic digestion (AD) control test. Each configuration was used on two operating scales (i.e., 120 ml and 12,000 ml reactor volume) to provide different data sets for the calibration and validation of the mathematical model proposed. The model calibration step was used to determine the optimal values of selected parameters displaying higher significance for experimental result predictability. The model calibration results highlighted a similar behavior for both BAD tests, which was further strengthened by a statistical analysis supporting the observed correlation regardless of the BAD configuration involved. The BAD configuration always enhanced the CH production (>70%) with a faster kinetic in the II-BAD test. The microbiological results support the superior performance of the II-BAD test, displaying higher Archaea fractions (up to 14.5% on day 23) with values more than double compared to I-BAD and triple compared to the AD test. Furthermore, the presence of Methanosarcina inside the Archaea guild (6.4% and 4.5% at days 11 and 61, respectively) ensures a greater diversification of the metabolic pathways and supports the strength of the process performance. Cell density values are strongly in line with these results.
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http://dx.doi.org/10.1016/j.scitotenv.2019.07.051DOI Listing
November 2019

Effect of sodium concentration on mobilization and fate of trace metals in standard OECD soil.

Environ Pollut 2019 Jul 19;250:839-848. Epub 2019 Apr 19.

Department of Civil, Architectural and Environmental Engineering, University of Naples Federico II, Via Claudio 21, 80125, Naples, Italy.

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.
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http://dx.doi.org/10.1016/j.envpol.2019.04.070DOI Listing
July 2019

Assessment of optimal conditions for the restoration and recovery of agricultural soil.

J Hazard Mater 2019 07 3;373:801-809. Epub 2019 Apr 3.

Department of Biology, University of Naples Federico II, Via Cinthia, 80126, Naples, Italy.

We assessed whether soil with high Cr contamination could be reclaimed by alkali, mineral, and organic acid-based ligands (OABLs) washing. We tested HNO, HSO, HCl, NaOH, HO, lactic acid (LA), malic acid (MA), oxalic acid (OA), and citric acid (CA), together with EDTA, obtaining the highest efficiencies in presence of 1 M sulfuric acid (98%). Nonetheless we noted that using OABLs, we obtained a Cr(III) removal efficiency similar to the one obtained using mineral acids. Indeed 1 M of LA and MA and 0.8 M of OA allowed obtaining, respectively, 88%, 75%, and 67% removal percentage. The extraction process with OABLs was strongly dependent on intraparticle diffusion of Cr-LA, Cr-MA, and Cr-OA complexes. We also determined the apparent diffusion coefficients. Residual toxicity of treated soils was tested with the nematode, Caenorhabditis elegans. The OABL washing generally allowed getting a soil without Cr and with reduced toxicity. However, the washing process also removed other cations that acted as nutrients. Consequently, we conducted toxicity tests on enriched soil and found that the mortality index improved. In some cases (LA and MA), mortality was comparable to that observed with uncontaminated control samples. In contrast, when contaminated soils were washed with sulfuric acid, in all conditions, we observed significant ecotoxicity. Therefore, we concluded that only the OABL treatment provided a non-toxic soil that could be reused for anthropic activities.
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http://dx.doi.org/10.1016/j.jhazmat.2019.04.007DOI Listing
July 2019

Evaluation of the potential for caesium transfer from contaminated soil to the food chain as a consequence of uptake by edible vegetables.

Ecotoxicol Environ Saf 2019 Apr 11;171:558-563. Epub 2019 Jan 11.

Czech University of Life Sciences Prague, Faculty of Environmental Sciences, Kamýcká 129, 165 21 Prague 6, Czech Republic.

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 KSO. Increasing concentrations of K lead to lower translocation of Cs from roots to leaves. Values above the average amount applied (20 and 40 mM KSO) almost stop the translocation, suggesting the use of a high amount of KSO protects the food chain from Cs contamination.
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http://dx.doi.org/10.1016/j.ecoenv.2019.01.015DOI Listing
April 2019

Porous Waste Glass for Lead Removal in Packed Bed Columns and Reuse in Cement Conglomerates.

Materials (Basel) 2018 Dec 28;12(1). Epub 2018 Dec 28.

Istituto di Nanotecnologia (Nanotec), Consiglio Nazionale delle Ricerche (CNR), c/o Dipartimento di Chimica, Università degli Studi di Bari "Aldo Moro", Via E. Orabona, 4, 70125 Bari, Italy.

A porous waste glass (RWPG = recycled waste porous glass) was used in wastewater treatments for the removal of lead ions from single, binary, and ternary metal solutions (with cadmium and nickel ions). Experiments were performed in columns (30 cm³, 10 g) filled with 0.5⁻1 mm beads till complete glass exhaustion (breakthrough). In the case of single and binary solutions, the columns were percolated at 0.2 Lh (2 mg Me L); in the case of ternary solutions, the columns were percolated at 0.15⁻0.4 Lh (2 mg Me L) and with 2⁻5 mg Me L influent concentration (0.2 Lh). Lead ions were removed mainly by ion exchange and also by adsorption. From a kinetic point of view, the rate controlling step of the process was the interdiffusion of the lead ions in the Nernst stationary liquid film around the sorbent. The uptake of the metals and the glass selectivity were confirmed by Energy Dispersive X-ray spectroscopy (EDX) analysis. After lead retention process, glass beads were reused as lightweight aggregates for thermal insulating and environmental safe mortars.
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http://dx.doi.org/10.3390/ma12010094DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6337151PMC
December 2018

Optimization of Soil Washing to Reduce the Selenium Levels of Seleniferous Soil from Punjab, Northwestern India.

J Environ Qual 2018 11;47(6):1530-1537

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.
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http://dx.doi.org/10.2134/jeq2018.05.0187DOI Listing
November 2018

Sustainable bio-hydrothermal sequencing treatment for asbestos-cement wastes.

J Hazard Mater 2019 Feb 15;364:256-263. Epub 2018 Oct 15.

Dipartimento di Ingegneria Civile, Ambientale, Edile, del Territorio e di Chimica, Politecnico di Bari, Via E. Orabona, 4, 70125, Bari, Italy.

In this paper, the treatment of asbestos-cement waste (ACW) has been attempted by a dark fermentation (DF) pre-treatment followed by hydrothermal and anaerobic digestion (AD) treatments. During DF, glucose, employed as a biodegradable substrate, was mainly converted to H-rich biogas and organic acids (OAs). The latter caused the dissolution of the cement matrix and the partial structural collapse of chrysotile (white asbestos). To complete the chrysotile degradation, hydrothermal treatment of the DF effluents was performed under varying operating conditions (temperature, acid type, and load). After the addition of 5.0 g/L sulfuric acid, a temperature decrease, from 80 °C to 40 °C, slowed down the treatment. Similarly, at 100 °C, a decrease of sulfuric, lactic or malic acid load from 5.0 g/L to 1.0 g/L slowed down the process, regardless of acid type. The acid type did not affect the hydrothermal treatment but influenced the AD of the hydrothermal effluents. Indeed, when malic acid was used, the AD of the hydrothermally treated effluents resulted in the highest production of methane. At the end of the AD treatment, some magnesium ions derived from ACW dissolution participated in the crystallization of struvite, an ecofriendly phosphorous-based fertilizer.
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http://dx.doi.org/10.1016/j.jhazmat.2018.10.025DOI Listing
February 2019

Sequential application of soil washing and phytoremediation in the land of fires.

J Environ Manage 2018 Jan 16;206:1081-1089. Epub 2017 Dec 16.

University of Naples Federico II, Department of Civil, Architectural and Environmental Engineering, Via Claudio21, 80125 Napoli, Italy.

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) and Zn (∼250 mg kg). 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.
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http://dx.doi.org/10.1016/j.jenvman.2017.11.080DOI Listing
January 2018

Ethylenediamine-N,N'-Disuccinic Acid (EDDS)-Enhanced Flushing Optimization for Contaminated Agricultural Soil Remediation and Assessment of Prospective Cu and Zn Transport.

Int J Environ Res Public Health 2018 03 18;15(3). Epub 2018 Mar 18.

Department of Civil, Architectural and Environmental Engineering, University of Naples Federico II, via Claudio 21, 80125 Naples, Italy.

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-,'-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.
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http://dx.doi.org/10.3390/ijerph15030543DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5877088PMC
March 2018

Assessment of metal pollution in the Lambro Creek (Italy).

Ecotoxicol Environ Saf 2018 Feb 26;148:754-762. Epub 2017 Nov 26.

University of Naples Federico II, Department of Biology, Via Cinthia, 80126 Napoli, Italy.

This study assessed the effect of metal pollution in the Lambro Creek (Southern Italy). Water, sediment and biota were collected at six sampling sites (June) for metal concentration assessment (Cr, Cu, Ni, Pb and Zn). Sequential extraction was performed to determine the distribution of metals in different geochemical sediment fractions. The influence of pH and leaching time on the release of metals from sediment to the water column was investigated via remobilization tests. A battery of toxicity tests (Vibrio fischeri, Raphidocelis subcapitata, Phaeodactylum tricornutum, and Daphnia magna) with multi-endpoints (bioluminescence, growth inhibition, and immobilization) was used to determine the overall toxicity in sediment water extracts. The results showed that metals did not exceed the probable effect concentration levels, with Cr concentration exceeding the threshold effect concentration level at all sampling points except for the one closer to the source of the creek, suggesting potential negative effect on the biota. Considering the cumulative criterion unit, sediment contamination was moderate at all sampling sites, except for L3 and L5 where biota was exposed to a very high risk. With respect to sequential analysis, the most readily available fraction of metal can be generalised as Ni > Cr > Cu > Zn > Pb. For better understanding the fate of metals in the water-sediment environment, their biogeochemical cycles should also be investigated in small creeks including both fresh (watercourse) and saltwater (river mouth) sediments.
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http://dx.doi.org/10.1016/j.ecoenv.2017.11.041DOI Listing
February 2018

Applicability of alkaline precipitation for the recovery of EDDS spent solution.

Authors:
Marco Race

J Environ Manage 2017 Dec 12;203(Pt 1):358-363. Epub 2017 Aug 12.

Dipartimento di Ingegneria Civile, Edile ed Ambientale, Università di Napoli Federico II, 80125 Napoli, Italy. Electronic address:

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.
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http://dx.doi.org/10.1016/j.jenvman.2017.08.013DOI Listing
December 2017

Photocatalytic processes assisted by artificial solar light for soil washing effluent treatment.

Environ Sci Pollut Res Int 2017 Mar 5;24(7):6353-6360. Epub 2016 Apr 5.

Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione Industriale, Università di Napoli "Federico II", P.le V. Tecchio 80, 80125, Naples, Italy.

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-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.
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http://dx.doi.org/10.1007/s11356-016-6431-9DOI Listing
March 2017
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