Residence time effects on phase transformation of nanosilver in reduced soils

Residence time effects on phase transformation of silver nanoparticles (AgNPs) (15–50 nm, with and without polyvinylpyrrolidone (PVP) coating) were investigated in reducing soils using experimental geochemistry and synchrotron-based x-ray techniques. After 30 days of anaerobic incubation, a substantial fraction of PVP-coated AgNPs (15 nm) were transformed into Ag₂S and or humic acid (HA) complexed Ag(I), whereas only the HA fraction was dominant in uncoated AgNPs (50 nm). Several investigations recently reported that sulfidation of AgNPs to Ag₂S was the predominant mechanism controlling the fate of AgNP in soil–water environments. However, this investigation showed each AgNP underwent particle-specific chemical transformations to different end compounds after 30 days. Considering the small contribution of Ag(I) dissolution from all AgNPs (less than 5 %), we concluded that changes in solid-state chemical speciation of sorbed AgNPs was promoted by particle-specific interactions of NPs in soil chemical constituents, suggesting a critical role of soil absorbents in predicting the fate of AgNPs in terrestrial environments.     

Biosynthesis of silver nanoparticles using <Emphasis Type="Italic">Myristica fragrans</Emphasis> seed (nutmeg) extract and its antibacterial activity against multidrug-resistant (MDR) <Emphasis Type="Italic">Salmonella enterica</Emphasis> serovar Typhi isolates

Biosynthesis of nanoparticles has received increasing attention due its effective mode of action, eco-friendly preparation methodology, and less cytotoxicity. In the present study, silver nanoparticles (AgNPs) from aqueous seed extract of Myristica fragrans (nutmeg) were characterized. Gas chromatography–mass spectrometry (GC–MS) analysis revealed the presence of bioactive components acts as effective in reducing and capping agents for converting AgNO₃ to AgNPs. The UV-Vis absorption spectrum of the biologically reduced reaction mixture showed the surface plasmon peak at 420 nm, which is the characteristic peak of AgNPs. The functional molecules present in the M. fragrans seed extract and their interaction with the AgNPs were identified by the Fourier transform infrared spectroscopy (FT-IR) analysis. X-ray diffraction (XRD) analysis confirmed the face-centered cubic crystalline structure of metallic silver nanoparticle and diameter was calculated using Scherrer’s equation. Transmission electron microscope (TEM) image showed spherical shaped particles with an average size of 25 nm. The scanning electron microscopy–energy dispersive spectroscopy (SEM–EDS) confirmed the presence of elemental silver. The antibacterial activity of biosynthesized AgNPs was evaluated against multidrug-resistant (MDR) Salmonella enterica serovar Typhi (S. Typhi) according to agar well diffusion, MIC (minimum inhibitory concentration), and IC₅₀ (inhibitory concentration 50%). The results confirm that bacterial growth was significantly reduced in a dose-dependent manner. Further, the cytotoxic effect of biosynthesized AgNPs on rat spleenocytes was analyzed. Thus, it is suggested that the nutmeg-biosynthesized AgNPs could be a lead drug and used effectively to control the MDR S. Typhi, thereby reducing public health issues and environmental pollution.     

Titania-supported silver-based bimetallic nanoparticles as photocatalysts

Photocatalytic process has shown recently a great potential as an environmental friendly and clean remediation technology for organic pollutants in wastewater. This work described the synthesis of silver-based bimetallic nanoparticles using colloid chemistry and the subsequent immobilization onto titania to form composite photocatalytic materials (titania-supported Ag–Pt nanoparticles). The photocatalysts were characterized by X-ray diffraction, electron microscopy, and nitrogen physisorption. The catalytic activity of the photocatalysts was evaluated by photocatalytic degradation of phenol and 2-chlorophenol (2-CP) in synthetic wastewater solutions. The photocatalytic processes were conducted in a batch photoreactor containing appropriate solutions of phenol and 2-CP with UV irradiation of 450 W. UV-visible spectrophotometer was used for analyzing the concentration of phenol and 2-CP in solutions. Parameters affecting the photocatalytic process such as the solution pH, phenol and 2-CP concentrations, and catalyst concentration were investigated. The results obtained revealed that TiO₂-supported Ag/Pt nanoparticles showed a higher activity for UV-photocatalytic degradation of both phenol and 2-CP pollutants in the solution (as compared to the plain rutile TiO₂). The photodegradation processes were optimized by the 0.5-g/L catalyst with a pollutant concentration of 50 mg/L for all the samples. Complete degradation for both phenol and 2-CP was achieved after 120 min.     

Heterogeneous Fenton degradation of bisphenol A catalyzed by efficient adsorptive Fe3O4/GO nanocomposites

A new method for the degradation of bisphenol A (BPA) in aqueous solution was developed. The oxidative degradation characteristics of BPA in a heterogeneous Fenton reaction catalyzed by Fe₃O₄/graphite oxide (GO) were studied. Transmission electron microscopic images showed that the Fe₃O₄ nanoparticles were evenly distributed and were ～6 nm in diameter. Experimental results suggested that BPA conversion was affected by several factors, such as the loading amount of Fe₃O₄/GO, pH, and initial H₂O₂ concentration. In the system with 1.0 g L^?1 of Fe₃O₄/GO and 20 mmol L^?1 of H₂O₂, almost 90 % of BPA (20 mg L^?1) was degraded within 6 h at pH 6.0. Based on the degradation products identified by GC–MS, the degradation pathways of BPA were proposed. In addition, the reused catalyst Fe₃O₄/GO still retained its catalytic activity after three cycles, indicating that Fe₃O₄/GO had good stability and reusability. These results demonstrated that the heterogeneous Fenton reaction catalyzed by Fe₃O₄/GO is a promising advanced oxidation technology for the treatment of wastewater containing BPA.     

Continuous flow photo-Fenton treatment of ciprofloxacin in aqueous solutions using homogeneous and magnetically recoverable catalysts

The degradation of ciprofloxacin was studied in aqueous solutions by using a continuous flow homogeneous photo-Fenton process under simulated solar light. The effect of different operating conditions on the degradation of ciprofloxacin was investigated by changing the hydrogen peroxide (0–2.50 mM) and iron(II) sulphate (0–10 mg Fe L^?1) concentrations, as well as the pH (2.8–10), irradiance (0–750 W m^?2) and residence time (0.13–3.4 min) of the process. As expected, the highest catalytic activity in steady state conditions was achieved at acidic pH (2.8), namely 85 % of ciprofloxacin conversion, when maintaining the other variables constant (i.e. 2.0 mg L^?1 of iron(II), 2.50 mM of hydrogen peroxide, 1.8 min of residence time and 500 W m^?2 of irradiance). Additionally, magnetite magnetic nanoparticles (ca. 20 nm of average particle size) were synthesized, characterized and tested as a possible catalyst for this reaction. In this case, the highest catalytic activity was achieved at natural pH, namely a 55 % average conversion of ciprofloxacin in 1.8 min of residence time and under 500 W m^?2. Some of the photocatalytic activity was attributed to Fe²⁺ leaching from the magnetic nanoparticles to the solution.     

Reaction of silver nanoparticles in the disinfection process

This study investigated the dissolution, aggregation, and reaction kinetics of silver nanoparticles (AgNPs) with the three types of water disinfectants (ultraviolet, sodium hypochlorite, and ozone) under the different conditions of pH, ionic strength, or humic acid (HA). The physicochemical changes of AgNPs were measured by using UV–Vis spectroscopy, transmission electron microscopy, and inductively coupled plasma optical emission spectrometer. The results showed that when AgNPs contacted the disinfectants, oxidative dissolution was the primary reaction. In addition, the reaction kinetics studies revealed that the reaction rate of AgNPs with disinfectants was significantly influenced by different disinfectants along with different pH and the presence of sodium nitrate and HA. Our research demonstrated the potential effect of disinfectants on AgNPs, which will improve our understanding of the fate of AgNPs in the disinfection processes in the water and wastewater treatment plant.     

Graphene—a promising material for removal of perchlorate (ClO4 −) from water

A batch adsorption process was applied to investigate the removal of perchlorate (ClO₄ ^?) from water by graphene. In doing so, the thermodynamic adsorption isotherm and kinetic studies were also carried out. Graphene was prepared by a facile liquid-phase exfoliation. Graphene was characterized by Raman spectroscopy, Fourier-transform infrared spectroscopy, powder X-ray diffraction, scanning electron microscope, and zeta potential measurements. A systematic study of the adsorption process was performed by varying pH, ionic strength, and temperature. The adsorption efficiency of graphene was 99.2 %, suggesting that graphene is an excellent adsorbent for ClO₄ ^? removal from water. The rate constants for all these kinetic models were calculated, and the results indicate that second-order kinetics model was well suitable to model the kinetic adsorption of ClO₄ ^?. Equilibrium data were well described by the typical Langmuir adsorption isotherm. The experimental results showed that graphene is an excellent perchlorate adsorbent with an adsorbent capacity of up to 0.024 mg/g at initial perchlorate concentration of 2 mg/L and temperature of 298 K. Thermodynamic studies revealed that the adsorption reaction was a spontaneous and endothermic process. Graphene removed the perchlorate present in the water and reduced it to a permissible level making it drinkable.     

Facile synthesis of magnetic ZnFe2O4–reduced graphene oxide hybrid and its photo-Fenton-like behavior under visible iradiation

A magnetic ZnFe₂O₄–reduced graphene oxide (rGO) hybrid was successfully developed as a heterogeneous catalyst for photo-Fenton-like decolorization of various dyes using peroxymonosulfate (PMS) as an oxidant under visible light irradiation. Through an in situ chemical deposition and reduction, ZnFe₂O₄ nanoparticles (NPs) with an average size of 23.7 nm were anchored uniformly on rGO sheets to form a ZnFe₂O₄–rGO hybrid. The catalytic activities in oxidative decomposition of organic dyes were evaluated. The reaction kinetics, effect of ion species and strength, catalytic stability, degradation mechanism, as well as the roles of ZnFe₂O₄ and graphene were also studied. ZnFe₂O₄–rGO showed to be a promising photocatalyst with magnetism for the oxidative degradation of aqueous organic pollutants and simple separation. The combination of ZnFe₂O₄ NPs with graphene sheets leads to a much higher catalytic activity than pure ZnFe₂O₄. Graphene acted as not only a support and stabilizer for ZnFe₂O₄ to prevent them from aggregation, largely improving the charge separation in the hybrid material, but also a catalyst for activating PMS to produce sulfate radicals at the same time. The ZnFe₂O₄–rGO hybrid exhibited stable performance without losing activity after five successive runs.     

Adsorption of ammonium on biochar prepared from giant reed

Giant reed was used as precursor for making biochar in order for the adsorption of NH₄ ⁺–N from aqueous solution. And the adsorption of the product to NH₄ ⁺–N was examined. The surface features of biochar were investigated by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy/energy dispersive spectrometer (SEM-EDS), and X-ray diffraction (XRD). XRD patterns showed several peaks and correspond to the high amount of crystalline material. The crystals contain KCl, K₂O, CaO, MgO, and SiO and possess high surface area which enhances adsorption. The influence of different parameters such as initial concentration, adsorption time, pH, and ionic strength has been carried out. The adsorption could reach equilibrium through 24 h reaction and had the best adsorption amount at the solution pH values from 7 to 9. The cation has great influence on the adsorption of NH₄ ⁺–N, whereas the anion exerted a weaker effect. The adsorption followed pseudo-first-order and pseudo-second-order models. And the intraparticle diffusion and desorption studies further elucidated that the mechanism of adsorption on the product was ion exchange. The product equilibrium data was well described by the Langmuir and Freundlich model. The maximum adsorption capacities were 1.490 mg/g. Biochar derived from giant reed at 500 °C was suggested as a promising adsorbent for the removal of NH₄ ⁺–N from slightly polluted wastewater.     

Electrosorption and photocatalytic one-stage combined process using a new type of nanosized TiO2/activated charcoal plate electrode

In the present study, an activated charcoal (AC) plate was prepared by physical activation method. Its surface was coated with TiO₂ nanoparticles by electrophoretic deposition (EPD) method. The average crystallite size of TiO₂ nanoparticles was determined approximately 28 nm. The nature of prepared electrode was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and Brunauer–Emmett–Teller (BET) surface area measurement before and after immobilization. The electrosorption and photocatalytic one-stage combined process was investigated in degradation of Lanasol Red 5B (LR5B), and the effect of dye concentration, electrolyte concentration, pH, voltage, and contact time was optimized and modeled using response surface methodology (RSM) approach. The dye concentration of 30 mg L^?1, Na₂SO₄ concentration of 4.38 g L^?1, pH of 4, voltage of 250 mV, and contact time of 120 min were determined as optimum conditions. Decolorization efficiency increased in combined process to 85.65 % at optimum conditions compared to 66.03 % in TiO₂/AC photocatalytic, 20.09 % in TiO₂/AC electrosorption, and 1.91 % in AC photocatalytic processes.     

Shape-dependent bactericidal activity of TiO2 for the killing of Gram-negative bacteria Agrobacterium tumefaciens under UV torch irradiation

This paper demonstrated the relative bactericidal activity of photoirradiated (6W-UV Torch, λ?>?340 nm and intensity?=?0.64 mW/cm²) P25–TiO₂ nanoparticles, nanorods, and nanotubes for the killing of Gram-negative bacterium Agrobacterium tumefaciens LBA4404 for the first time. TiO₂ nanorod (anatase) with length of 70–100 nm and diameter of 10–12 nm, and TiO₂ nanotube with length of 90–110 nm and diameter of 9–11 nm were prepared from P-25 Degussa TiO₂ (size, 30–50 nm) by hydrothermal method and compared their biocidal activity both in aqueous slurry and thin films. The mode of bacterial cell decomposition was analyzed through transmission electron microscopy (TEM), Fourier transform-infrared (FT-IR), and K⁺ ion leakage. The antimicrobial activity of photoirradiated TiO₂ of different shapes was found to be in the order P25–TiO₂?>?nanorod?>?nanotube which is reverse to their specific surface area as 54?<?79?<?176 m² g^?1, evidencing that the highest activity of P25–TiO₂ nanoparticles is not due to surface area as their crystal structure and surface morphology are entirely different. TiO₂ thin films always exhibited less photoactivity as compared to its aqueous suspension under similar conditions of cell viability test. The changes in the bacterial surface morphology by UV-irradiated P25–TiO₂ nanoparticles was examined by TEM, oxidative degradation of cell components such as proteins, carbohydrates, phospholipids, nucleic acids by FT-IR spectral analysis, and K⁺ ion leakage (2.5 ppm as compared to 0.4 ppm for control culture) as a measure of loss in cell membrane permeability.     

Photocatalytic degradation of contaminants of concern with composite NF-TiO2 films under visible and solar light

This study reports the synthesis and characterization of composite nitrogen and fluorine co-doped titanium dioxide (NF-TiO₂) for the removal of contaminants of concern in wastewater under visible and solar light. Monodisperse anatase TiO₂ nanoparticles of different sizes and Evonik P25 were assembled to immobilized NF-TiO₂ by direct incorporation into the sol–gel or by the layer-by-layer technique. The composite films were characterized with X-ray diffraction, high-resolution transmission electron microscopy, environmental scanning electron microscopy, and porosimetry analysis. The photocatalytic degradation of atrazine, carbamazepine, and caffeine was evaluated in a synthetic water solution and in an effluent from a hybrid biological concentrator reactor (BCR). Minor aggregation and improved distribution of monodisperse titania particles was obtained with NF-TiO₂-monodisperse (10 and 50 nm) from the layer-by-layer technique than with NF-TiO₂?+?monodisperse TiO₂ (300 nm) directly incorporated into the sol. The photocatalysts synthesized with the layer-by-layer method achieved significantly higher degradation rates in contrast with NF-TiO₂-monodisperse titania (300 nm) and slightly faster values when compared with NF-TiO₂-P25. Using NF-TiO₂ layer-by-layer with monodisperse TiO₂ (50 nm) under solar light irradiation, the respective degradation rates in synthetic water and BCR effluent were 14.6 and 9.5?×?10^?3?min^?1 for caffeine, 12.5 and 9.0?×?10^?3?min^?1 for carbamazepine, and 10.9 and 5.8?×?10^?3?min^?1 for atrazine. These results suggest that the layer-by-layer technique is a promising method for the synthesis of composite TiO₂-based films compared to the direct addition of nanoparticles into the sol.     

Toxicity,uptake, and accumulation of nano and bulk cerium oxide particles in <Emphasis Type="Italic">Artemia salina</Emphasis>

Although the toxicological impact of metal oxide nanoparticles has been studied for the last few decades on aquatic organisms, the exact mechanism of action is still unclear. The fate, behavior, and biological activity of nanoparticles are dependent on physicochemical factors like size, shape, surface area, and stability in the medium. This study deals with the effect of nano and bulk CeO₂ particles on marine microcrustacean, Artemia salina. The primary size was found to be 15 ± 3.5 and 582 ± 50 nm for nano and bulk CeO₂ (TEM), respectively. The colloidal stability and sedimentation assays showed rapid aggregation of bulk particles in seawater. Both the sizes of CeO₂ particles inhibited the hatching rate of brine shrimp cyst. Nano CeO₂ was found to be more toxic to A. salina (48 h LC₅₀ 38.0 mg/L) when compared to bulk CeO₂ (48 h LC₅₀ 92.2 mg/L). Nano CeO₂-treated A. salina showed higher oxidative stress (ROS) than those treated with the bulk form. The reduction in the antioxidant activity indicated an increase in oxidative stress in the cells. Higher acetylcholinesterase activity (AChE) was observed upon exposure to nano and bulk CeO₂ particles. The uptake and accumulation of CeO₂ particles were increased with respect to the concentration and particle size. Thus, the above results revealed that nano CeO₂ was more lethal to A. salina as compared to bulk particles.     

Green synthesis of gold nanoparticles using fungus <Emphasis Type="Italic">Mariannaea</Emphasis> sp. HJ and their catalysis in reduction of 4-nitrophenol

In the present study, biosynthesis of gold nanoparticles (AuNPs) by the cells (cells-AuNPs) and cell-free extracts (extracts-AuNPs) of a new fungus Mariannaea sp. HJ was reported. The as-synthesized particles were characterized by UV-vis spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). The effects of different parameters on AuNP biosynthesis were investigated, and initial gold ion concentration of 2 mM, pH 7, was demonstrated to be suitable for both cells-AuNP and extracts-AuNP syntheses. The cells-AuNPs were of various shapes, including sphere, hexagon, and irregular shapes, with an average size of 37.4 nm, while the extracts-AuNPs were almost spherical and pseudo-spherical with an average size of 11.7 nm. XRD pattern suggested that the crystal structure of both AuNPs was face-centered cubic. FTIR spectra implied that some biomolecules from the fungal cell walls or cell-free extracts were involved in the formation of AuNPs. The as-synthesized AuNPs were demonstrated to have excellent catalytic activities for the reduction of 4-nitrophenol with the catalytic rate constants of 5.7 × 10^?3/s for cells-AuNPs and 24.7 × 10^?3/s for extracts-AuNPs. To the best of our knowledge, this is the first report on AuNP biosynthesis by Mariannaea sp.     

Photocatalytic degradation of acetaminophen in modified TiO2 under visible irradiation

This study investigated the photocatalytic degradation of acetaminophen (ACT) in synthetic titanium dioxide (TiO₂) solution under a visible light (λ >440 nm). The TiO₂ photocatalyst used in this study was synthesized via sol–gel method and doped with potassium aluminum sulfate (KAl(SO₄)₂) and sodium aluminate (NaAlO₂). The influence of some parameters on the degradation of acetaminophen was examined, such as initial pH, photocatalyst dosage, and initial ACT concentration. The optimal operational conditions were also determined. Results showed that synthetic TiO₂ catalysts presented mainly as anatase phase and no rutile phase was observed. The results of photocatalytic degradation showed that LED alone degraded negligible amount of ACT but with the presence of TiO₂/KAl(SO₄)₂, 95 % removal of 0.10-mM acetaminophen in 540-min irradiation time was achieved. The synthetic TiO₂/KAl(SO₄)₂ presented better photocatalytic degradation of acetaminophen than commercially available Degussa P-25. The weak crystallinity of synthesized TiO₂/NaAlO₂ photocatalyst showed low photocatalytic degradation than TiO₂/KAl(SO₄)₂. The optimal operational conditions were obtained in pH 6.9 with a dose of 1.0 g/L TiO₂/KAl(SO₄)₂ at 30 °C. Kinetic study illustrated that photocatalytic degradation of acetaminophen fits well in the pseudo-first order model. Competitive reactions from intermediates affected the degradation rate of ACT, and were more obvious as the initial ACT concentration increased.     

Rapid biological synthesis of silver nanoparticles using <Emphasis Type="Italic">Leucas martinicensis</Emphasis> leaf extract for catalytic and antibacterial activity

A novel green approach for the synthesis and stabilization of silver nanoparticles (AgNPs) using water extract of Leucas martinicensis leaf has been developed. As obtained, the nanoparticles are characterized by UV-visible (UV-Vis), transmission electron microscope (TEM), and X-ray diffraction (XRD). The crystalline nature of the AgNPs is confirmed by the prominent peaks in the XRD pattern. FTIR spectra suggest that the possible biomolecules are responsible for the efficient stabilization of the sample. The effects of leaf quantity on the biosynthesis of AgNPs are investigated by UV-Vis spectrophotometer. The synthesized AgNPs are observed to have a good catalytic activity on the reduction of methylene blue by L. martinicensis leaf. This is confirmed by the decrease in absorbance maximum values of methylene blue with respect to time through UV-Vis spectrophotometer. Moreover, the antibacterial activity of synthesized AgNPs against Staphylococcus aureus, Bacillus subtilis, Salmonella typhi, and Escherichia coli are screened.     

Oxidized multiwalled carbon nanotubes as adsorbent for the removal of manganese from aqueous solution

A batch adsorption process was applied to investigate the removal of manganese from aqueous solution by oxidized multiwalled carbon nanotubes (MWCNTs). In doing so, the thermodynamic, adsorption isotherm, and kinetic studies were also carried out. MWCNT with 5–10-nm outer diameter, surface area of 40–600 m²/g, and purity above 95 % was used as an adsorbent. A systematic study of the adsorption process was performed by varying pH, ionic strength, and temperature. Manganese-adsorbed MWCNT was characterized by Raman, FTIR, X-ray diffraction, XPS, SEM, and TEM. The adsorption efficiency could reach 96.82 %, suggesting that MWCNT is an excellent adsorbent for manganese removal from water. The results indicate that second-order kinetics model was well suitable to model the kinetic adsorption of manganese. Equilibrium data were well described by the typical Langmuir adsorption isotherm. Thermodynamic studies revealed that the adsorption reaction was spontaneous and endothermic process. The experimental results showed that MWCNT is an excellent manganese adsorbent. The MWCNTs removed the manganese present in the water and reduced it to a permissible level making it drinkable.     

Rapid dye degradation with reactive oxidants generated by chloride-induced peroxymonosulfate activation

Transition-metal is known to catalyze peroxymonosulfate (PMS) decomposition to produce sulfate radicals. Here we report reactions between PMS and chloride, without a need of transition metals, also can be used to degrade organic dye pollutant (Rhodamine B, (RhB)). Some important operating parameters, such as dosages of PMS and Cl^?, pH of solution, temperature, ionic strength, and several common cations, were systematically investigated. Almost complete decoloration of RhB was achieved within 5 min ([PMS]?=?0.5 mM, [Cl^?]?=?120 mM, and pH 3.0), and RhB bleaching rate increased with the increased dosages of both PMS and chloride ion, following the pseudo-first-order kinetic model. However, the total organic carbon (TOC) removal results demonstrated that the decoloration of RhB was due to the destruction of chromophore rather than complete degradation. RhB decoloration could be significantly accelerated due to the high ionic strength. Increasing of the reaction temperature from 273 K to 333 K was beneficial to the RhB degradation, and the activation energy was determined to be 32.996 kJ/mol. Bleaching rate of RhB with the examined cations increased with the order of NH₄ ⁺?<?Na⁺?<?K⁺?<?Al³⁺?<?Ca²⁺?<?Mg²⁺. Some major degradation products of RhB were identified by GC-MS. The present study may have active technical implications for the treatment of dyestuff wastewater in practice.     

Stability of titania nanoparticles in soil suspensions and transport in saturated homogeneous soil columns

The stability of TiO₂ nanoparticles in soil suspensions and their transport behavior through saturated homogeneous soil columns were studied. The results showed that TiO₂ could remain suspended in soil suspensions even after settling for 10 days. The suspended TiO₂ contents in soil suspensions after 24 h were positively correlated with the dissolved organic carbon and clay content of the soils, but were negatively correlated with ionic strength, pH and zeta potential. In soils containing soil particles of relatively large diameters and lower solution ionic strengths, a significant portion of the TiO₂ (18.8-83.0%) readily passed through the soils columns, while TiO₂ was significantly retained by soils with higher clay contents and salinity. TiO₂ aggregate sizes in the column outflow significantly increased after passing through the soil columns. The estimated transport distances of TiO₂ in some soils ranged from 41.3 to 370 cm, indicating potential environmental risk of TiO₂ nanoparticles to deep soil layers.     

Removal of PCBs in contaminated soils by means of chemical reduction and advanced oxidation processes

Although the chemical reduction and advanced oxidation processes have been widely used individually, very few studies have assessed the combined reduction/oxidation approach for soil remediation. In the present study, experiments were performed in spiked sand and historically contaminated soil by using four synthetic nanoparticles (Fe⁰, Fe/Ni, Fe₃O₄, Fe_3???x Ni _x O₄). These nanoparticles were tested firstly for reductive transformation of polychlorinated biphenyls (PCBs) and then employed as catalysts to promote chemical oxidation reactions (H₂O₂ or persulfate). Obtained results indicated that bimetallic nanoparticles Fe/Ni showed the highest efficiency in reduction of PCB28 and PCB118 in spiked sand (97 and 79 %, respectively), whereas magnetite (Fe₃O₄) exhibited a high catalytic stability during the combined reduction/oxidation approach. In chemical oxidation, persulfate showed higher PCB degradation extent than hydrogen peroxide. As expected, the degradation efficiency was found to be limited in historically contaminated soil, where only Fe⁰ and Fe/Ni particles exhibited reductive capability towards PCBs (13 and 18 %). In oxidation step, the highest degradation extents were obtained in presence of Fe⁰ and Fe/Ni (18–19 %). The increase in particle and oxidant doses improved the efficiency of treatment, but overall degradation extents did not exceed 30 %, suggesting that only a small part of PCBs in soil was available for reaction with catalyst and/or oxidant. The use of organic solvent or cyclodextrin to improve the PCB availability in soil did not enhance degradation efficiency, underscoring the strong impact of soil matrix. Moreover, a better PCB degradation was observed in sand spiked with extractable organic matter separated from contaminated soil. In contrast to fractions with higher particle size (250–500 and <500 μm), no PCB degradation was observed in the finest fraction (≤250 μm) having higher organic matter content. These findings may have important practical implications to promote successively reduction and oxidation reactions in soils and understand the impact of soil properties on remediation performance.