The usage of reclaimed wastewater (RWW) for irrigation of agricultural soils is increasingly bein... more The usage of reclaimed wastewater (RWW) for irrigation of agricultural soils is increasingly being acknowledged for reducing water consumption by promoting reuse of treated wastewater, and for the delivery of extant nutrients in the soil. The downside is that RWW may be a vector for contamination of soils with contaminants of emerging concern (CECs), if left uncontrolled. Its usage is anticipated to alter the soil properties, consequently also the soil microbial community. In the present study, soil microcosms were set to monitor how short periods (up to fourteen days) of RWW irrigation influence the soil ecosystem, namely its physicochemical properties, functioning, and colonising microbiota (differentiating fungi from bacteria). Two scenarios were studied: clean soil and soil contaminated (spiked) with 9 CECs, at conditions that limit any abiotic decay processes, monitoring along time fluctuations in the taxonomic and functional microbiota diversity. As shortly as fourteen days, the irrigation of either soil with RWW did not significantly (p > 0.05) alter its physicochemical properties and scarcely impacted the bioremediation processes of the CECs that showed decay levels ranging from 24% to 100%. Bacillus spp. dominance was enhanced along time in all the soil microcosms (reaching over 70% of the total abundance on the 7th day) but the RWW help to preserve, to some extent, high bacterial diversity. Besides, irrigation with RWW acted as a buffer of the soil mycobiota, limiting alterations in its composition caused either along time (to a minor degree) or due to contamination with CECs (to a great degree). This includes limiting the rise of Rhizopus sp. relative abundance. Collectively, our data support the utility of short-term periods of RWW irrigation for preserving the soil microbial diversity and functioning, especially when fungi are considered.
Zero valent iron nanoparticles (nZVI) transport for soil and groundwater remediation is slowed do... more Zero valent iron nanoparticles (nZVI) transport for soil and groundwater remediation is slowed down or halted by aggregation or fast depletion in the soil pores. Direct electric current can enhance the transport of nZVI in low permeability soils. However operational factors, including pH, oxidation-reduction potential (ORP), voltage and ionic strength of the electrolyte can play an important role in the treatment effectiveness. Experiments were conducted to enhance polymer coated nZVI mobility in a model low permeability soil medium (kaolin clay) using low direct current. Different electrolytes of varying ionic strengths and initial pH and high nZVI concentrations were applied. Results showed that the nZVI transport is enhanced by direct current, even considering concentrations typical of field application that favor nanoparticle aggregation. However, the factors considered (pH, ORP, voltage and electrolyte) failed to explain the iron concentration variation. The electrolyte and its ionic strength proved to be significant for pH and ORP measured during the experiments, and therefore will affect aggregation and fast oxidation of the particles.
ABSTRACT One of the major obstacles to zerovalent iron nanoparticles (nZVI) application in soil a... more ABSTRACT One of the major obstacles to zerovalent iron nanoparticles (nZVI) application in soil and groundwater remediation is the limited transport, especially in low-permeability soils. In this study, direct current (constant potential of 5.0 V) was used to enhance polymer-coated nZVI mobility in different porous media, including a bed of glass beads and kaolin clay. The tests were conducted using a modified electrophoretic cell and with nZVI concentrations typical of field applications (4 g L−1). Experimental results indicate that the use of direct current can enhance the transport of the polymer-modified nanoparticles when compared with natural diffusion in low permeability or surface neutral porous medium. The applied electric field appeared to enhance the oxidation–reduction potential, creating a synergistic effect of nZVI usage with electrokinetics. Aggregation of the nanoparticles, observed near the injection point, remained unresolved.
Polychlorinated biphenyls (PCB) are carcinogenic and persistent organic pollutants that accumulat... more Polychlorinated biphenyls (PCB) are carcinogenic and persistent organic pollutants that accumulate in soils and sediments. Currently, there is no cost-effective and sustainable remediation technology for these contaminants. In this work, a new combination of electrodialytic remediation and zero valent iron particles in a two-compartment cell is tested and compared to a more conventional combination of electrokinetic remediation and nZVI in a three-compartment cell. In the new two-compartment cell, the soil is suspended and stirred simultaneously with the addition of zero valent iron nanoparticles. Remediation experiments are made with two different historically PCB contaminated soils, which differ in both soil composition and contamination source. Soil 1 is a mix of soils with spills of transformer oils, while Soil 2 is a superficial soil from a decommissioned school where PCB were used as windows sealants. Saponin, a natural surfactant, was also tested to increase the PCB desorption from soils and enhance dechlorination. Remediation of Soil 1 (with highest pH, carbonate content, organic matter and PCB concentrations) obtained the maximum 83% and 60% PCB removal with the two-compartment and the three-compartment cell, respectively. The highest removal with Soil 2 were 58% and 45%, in the two-compartment and the three-compartment cell, respectively, in the experiments without direct current. The pH of the soil suspension in the two-compartment treatment appears to be a determining factor for the PCB dechlorination, and this cell allowed a uniform distribution of the nanoparticles in the soil, while there was iron accumulation in the injection reservoir in the three-compartment cell.
ABSTRACT Due to their abundance in the natural environment, chloride, nitrate and sulfate salts a... more ABSTRACT Due to their abundance in the natural environment, chloride, nitrate and sulfate salts are considered the main responsible for the salt-induced decay processes in building materials and sculptures. Electro-desalination techniques, enhanced with carbonated clay buffer poultice placed between the surface of the stone and the electrodes, have been successfully applied for the prevention of salt-induced deterioration problems of masonry and other construction materials. However, it has been experimentally observed that, in this type of treatments, the removal rate of sulfates is considerably slower than chlorides and nitrates.A physicochemical model for electrochemically induced reactive-transport processes is described and used for a theoretical analysis of the influence of the chemical interactions on the removal rate of the target ions. Simulations for the electro-desalination of a brick sample contaminated with a combination of these target ions are shown. Results from simulations show that the lower removal efficiency of sulfates is related to the precipitation of gypsum inside the porous body. Modifications of the existing technique are suggested based on the simulation results.
Electrokinetic processes are known as the mobilization of species within the pore solution of por... more Electrokinetic processes are known as the mobilization of species within the pore solution of porous materials under the effect of an external electric field. A finite elements model was implemented and used for the integration of the coupled Nernst-Plank-Poisson system of equations in order to simulate the transport process of ionic species and the modeling of electrokinetic remediation techniques. The electrode half-reactions were included in the model. The charge unbalance produced was used for satisfying the voltage differences applied as boundary conditions in the system. In addition to this, water equilibrium was continuously assured and the pH value monitored. Results from a test example simulation of the desalination of a sample of porous material contaminated with NaCl are shown.
The usage of reclaimed wastewater (RWW) for irrigation of agricultural soils is increasingly bein... more The usage of reclaimed wastewater (RWW) for irrigation of agricultural soils is increasingly being acknowledged for reducing water consumption by promoting reuse of treated wastewater, and for the delivery of extant nutrients in the soil. The downside is that RWW may be a vector for contamination of soils with contaminants of emerging concern (CECs), if left uncontrolled. Its usage is anticipated to alter the soil properties, consequently also the soil microbial community. In the present study, soil microcosms were set to monitor how short periods (up to fourteen days) of RWW irrigation influence the soil ecosystem, namely its physicochemical properties, functioning, and colonising microbiota (differentiating fungi from bacteria). Two scenarios were studied: clean soil and soil contaminated (spiked) with 9 CECs, at conditions that limit any abiotic decay processes, monitoring along time fluctuations in the taxonomic and functional microbiota diversity. As shortly as fourteen days, the irrigation of either soil with RWW did not significantly (p > 0.05) alter its physicochemical properties and scarcely impacted the bioremediation processes of the CECs that showed decay levels ranging from 24% to 100%. Bacillus spp. dominance was enhanced along time in all the soil microcosms (reaching over 70% of the total abundance on the 7th day) but the RWW help to preserve, to some extent, high bacterial diversity. Besides, irrigation with RWW acted as a buffer of the soil mycobiota, limiting alterations in its composition caused either along time (to a minor degree) or due to contamination with CECs (to a great degree). This includes limiting the rise of Rhizopus sp. relative abundance. Collectively, our data support the utility of short-term periods of RWW irrigation for preserving the soil microbial diversity and functioning, especially when fungi are considered.
Zero valent iron nanoparticles (nZVI) transport for soil and groundwater remediation is slowed do... more Zero valent iron nanoparticles (nZVI) transport for soil and groundwater remediation is slowed down or halted by aggregation or fast depletion in the soil pores. Direct electric current can enhance the transport of nZVI in low permeability soils. However operational factors, including pH, oxidation-reduction potential (ORP), voltage and ionic strength of the electrolyte can play an important role in the treatment effectiveness. Experiments were conducted to enhance polymer coated nZVI mobility in a model low permeability soil medium (kaolin clay) using low direct current. Different electrolytes of varying ionic strengths and initial pH and high nZVI concentrations were applied. Results showed that the nZVI transport is enhanced by direct current, even considering concentrations typical of field application that favor nanoparticle aggregation. However, the factors considered (pH, ORP, voltage and electrolyte) failed to explain the iron concentration variation. The electrolyte and its ionic strength proved to be significant for pH and ORP measured during the experiments, and therefore will affect aggregation and fast oxidation of the particles.
ABSTRACT One of the major obstacles to zerovalent iron nanoparticles (nZVI) application in soil a... more ABSTRACT One of the major obstacles to zerovalent iron nanoparticles (nZVI) application in soil and groundwater remediation is the limited transport, especially in low-permeability soils. In this study, direct current (constant potential of 5.0 V) was used to enhance polymer-coated nZVI mobility in different porous media, including a bed of glass beads and kaolin clay. The tests were conducted using a modified electrophoretic cell and with nZVI concentrations typical of field applications (4 g L−1). Experimental results indicate that the use of direct current can enhance the transport of the polymer-modified nanoparticles when compared with natural diffusion in low permeability or surface neutral porous medium. The applied electric field appeared to enhance the oxidation–reduction potential, creating a synergistic effect of nZVI usage with electrokinetics. Aggregation of the nanoparticles, observed near the injection point, remained unresolved.
Polychlorinated biphenyls (PCB) are carcinogenic and persistent organic pollutants that accumulat... more Polychlorinated biphenyls (PCB) are carcinogenic and persistent organic pollutants that accumulate in soils and sediments. Currently, there is no cost-effective and sustainable remediation technology for these contaminants. In this work, a new combination of electrodialytic remediation and zero valent iron particles in a two-compartment cell is tested and compared to a more conventional combination of electrokinetic remediation and nZVI in a three-compartment cell. In the new two-compartment cell, the soil is suspended and stirred simultaneously with the addition of zero valent iron nanoparticles. Remediation experiments are made with two different historically PCB contaminated soils, which differ in both soil composition and contamination source. Soil 1 is a mix of soils with spills of transformer oils, while Soil 2 is a superficial soil from a decommissioned school where PCB were used as windows sealants. Saponin, a natural surfactant, was also tested to increase the PCB desorption from soils and enhance dechlorination. Remediation of Soil 1 (with highest pH, carbonate content, organic matter and PCB concentrations) obtained the maximum 83% and 60% PCB removal with the two-compartment and the three-compartment cell, respectively. The highest removal with Soil 2 were 58% and 45%, in the two-compartment and the three-compartment cell, respectively, in the experiments without direct current. The pH of the soil suspension in the two-compartment treatment appears to be a determining factor for the PCB dechlorination, and this cell allowed a uniform distribution of the nanoparticles in the soil, while there was iron accumulation in the injection reservoir in the three-compartment cell.
ABSTRACT Due to their abundance in the natural environment, chloride, nitrate and sulfate salts a... more ABSTRACT Due to their abundance in the natural environment, chloride, nitrate and sulfate salts are considered the main responsible for the salt-induced decay processes in building materials and sculptures. Electro-desalination techniques, enhanced with carbonated clay buffer poultice placed between the surface of the stone and the electrodes, have been successfully applied for the prevention of salt-induced deterioration problems of masonry and other construction materials. However, it has been experimentally observed that, in this type of treatments, the removal rate of sulfates is considerably slower than chlorides and nitrates.A physicochemical model for electrochemically induced reactive-transport processes is described and used for a theoretical analysis of the influence of the chemical interactions on the removal rate of the target ions. Simulations for the electro-desalination of a brick sample contaminated with a combination of these target ions are shown. Results from simulations show that the lower removal efficiency of sulfates is related to the precipitation of gypsum inside the porous body. Modifications of the existing technique are suggested based on the simulation results.
Electrokinetic processes are known as the mobilization of species within the pore solution of por... more Electrokinetic processes are known as the mobilization of species within the pore solution of porous materials under the effect of an external electric field. A finite elements model was implemented and used for the integration of the coupled Nernst-Plank-Poisson system of equations in order to simulate the transport process of ionic species and the modeling of electrokinetic remediation techniques. The electrode half-reactions were included in the model. The charge unbalance produced was used for satisfying the voltage differences applied as boundary conditions in the system. In addition to this, water equilibrium was continuously assured and the pH value monitored. Results from a test example simulation of the desalination of a sample of porous material contaminated with NaCl are shown.
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