Emerging technologies for the removal of pesticides from contaminated soils and their reuse in agriculture.

Pesticides are becoming more prevalent in agriculture to protect crops and increase crop yields. However, nearly all pesticides used for this purpose reach non-target crops and remain as residues for extended periods. Contamination of soil by widespread pesticide use, as well as its toxicity to humans and other living organisms, is a global concern. This has prompted us to find solutions and develop alternative remediation technologies for sustainable management. This article reviews recent technological developments for remediating pesticides from contaminated soil, focusing on the following major points: (1) The application of various pesticide types and their properties, the sources of pesticides related to soil pollution, their transport and distribution, their fate, the impact on soil and human health, and the extrinsic and intrinsic factors that affect the remediation process are the main points of focus. (2) Sustainable pesticide degradation mechanisms and various emerging nano- and bioelectrochemical soil remediation technologies. (3) The feasible and long-term sustainable research and development approaches that are required for on-site pesticide removal from soils, as well as prospects for applying them directly in agricultural fields. In this critical analysis, we found that bioremediation technology has the potential for up to 90% pesticide removal from the soil. The complete removal of pesticides through a single biological treatment approach is still a challenging task; however, the combination of electrochemical oxidation and bioelectrochemical system approaches can achieve the complete removal of pesticides from soil. Further research is required to remove pesticides directly from soils in agricultural fields on a large-scale.

Heterogeneous photocatalytic activation of electrogenerated chlorine for the production of reactive oxygen and chlorine species: A new approach for Bisphenol A degradation in saline wastewater.

UV-E-chlorination/hematite nanoparticles (UV/E-Cl/HNs) as a heterogeneous photocatalytic activation of electrogenerated chlorine was assessed for the degradation of bisphenol A (BPA) as a new approach based on the generation of reactive chlorine and oxygen species. The prepared sample was characterized using multiple techniques, such as XRD, FTIR, FESEM, EDS, and BET-BJH. An excellent decontamination efficiency of 99.4% was achieved within 40 min of electrolysis under optimum conditions (pH of 5, HNs dosage 100 mg/L, current density of 20 mA/cm2, and NaCl concentration of 50 mM). The HOCl content was reduced more swiftly in the presence of ultraviolet (UV) irradiation and hematite, resulting in the production of oxidative radicals (i.e., •OH, Cl•, and Cl2•-). The scavenging experiments also verified the vital role of these radicals in oxidative treatment. The UV/E-Cl/HNs process is readily supplied with hydroxyl radicals through several mechanisms. Bicarbonate ions showed a noticeable inhibitory impact, whereas nitrate and sulfate anions only slightly affected BPA degradation. The HNs were a recoverable and stable catalyst for six cycles. Furthermore, the ECOSAR program predicted that the UV/E-Cl/HNs can be labeled as an environmental-friendly process. Eventually, reasonable degradation pathways were proposed based on the identified by-products through experimental and theoretical approaches.

Waste to catalyst: Role of agricultural waste in water and wastewater treatment.

Presently, owing to the rapid development of industrialization and urbanization activities, a huge quantity of wastewater is generated that contain toxic chemical and heavy metals, imposing higher environmental jeopardies and affecting the life of living well-being and the economy of the counties, if not treated appropriately. Subsequently, the advancement in sustainable cost-effective wastewater treatment technology has attracted more attention from policymakers, legislators, and scientific communities. Therefore, the current review intends to highlight the recent development and applications of biochars and/or green nanoparticles (NPs) produced from agricultural waste via green routes in removing the refractory pollutants from water and wastewater. This review also highlights the contemporary application and mechanism of biochar-supported advanced oxidation processes (AOPs) for the removal of organic pollutants in water and wastewater. Although, the fabrication and application of agriculture waste-derived biochar and NPs are considered a greener approach, nevertheless, before scaling up production and application, its toxicological and life-cycle challenges must be taken into account. Furthermore, future efforts should be carried out towards process engineering to enhance the performance of green catalysts to improve the economy of the process.

Sulfate radicals-based advanced oxidation processes for the degradation of pharmaceuticals and personal care products: A review on relevant activation mechanisms, performance, and perspectives.

Owing to the rapid development of modern industry, a greater number of organic pollutants are discharged into the water matrices. In recent decades, research efforts have focused on developing more effective technologies for the remediation of water containing pharmaceuticals and personal care products (PPCPs). Recently, sulfate radicals-based advanced oxidation processes (SR-AOPs) have been extensively used due to their high oxidizing potential, and effectiveness compared with other AOPs in PPCPs remediation. The present review provides a comprehensive assessment of the different methods such as heat, ultraviolet (UV) light, photo-generated electrons, ultrasound (US), electrochemical, carbon nanomaterials, homogeneous, and heterogeneous catalysts for activating peroxymonosulfate (PMS) and peroxydisulfate (PDS). In addition, possible activation mechanisms from the point of radical and non-radical pathways are discussed. Then, biodegradability enhancement and toxicity reduction are highlighted. Comparison with other AOPs and treatment of PPCPs by the integrated process are evaluated as well. Lastly, conclusions and future perspectives on this research topic are elaborated.

Recent progress on ultrasound-assisted electrochemical processes: A review on mechanism, reactor strategies, and applications for wastewater treatment.

The electrochemical advanced oxidation processes (EAOPs) have received significant attention among the many other water and wastewater treatment technologies. However, achieving a desirable removal effect with a single technique is frequently difficult. Therefore, the integration of ultrasound technique with other processes such as electrocoagulation, electro-Fenton, and electrooxidation is a critical way to achieve effective organic pollutants decomposition from wastewater. This review paper is focused on ultrasound-assisted electrochemical (US/electrochemical) processes, so-called sonoelectrochemical processes of various organic pollutants. Emphasis was given to recently published articles for discussing the results and trends in this research area. The use of ultrasound and integration with electrochemical processes has a synergistic impact owing to the physical and chemical consequences of cavitation, resulting in enhancing the mineralization of organic pollutants. Various types of sonoelectrochemical reactors (batch and continuous) employed in the US/electrochemical processes were reviewed. In addition, the strategies to avoid passivation, enhanced generation of reactive oxygen species, and mixing effect are reviewed. Finally, concluding remarks and future perspectives on this research topic are also explored and recommended.

Electrochemical activation of peroxides for treatment of contaminated water with landfill leachate: Efficacy, toxicity and biodegradability evaluation.

Contaminated water with landfill leachate (CWLL) with high salinity and high organic content (total organic carbon (TOC) = 649 mg/L and Chemical Oxygen Demand (COD) = 1175 mg/L) is a toxic and non-biodegradable effluent. The present research aimed to assess the treatment effectiveness of CWLL by electrocoagulation (EC)/oxidant process. The ferrous ions generated during the process were employed as coagulant and catalyst for the activation of different oxidants such as peroxymonosulfate (PMS), peroxydisulfate (PDS), hydrogen peroxide (HP), and percarbonate (PC) to decrease TOC in CWLL. Removal of ammonia, color, phosphorous, and chemical oxygen demand (COD) from CWLL effluent was explored at various processes. EC/HP had the best performance (∼73%) in mineralization of organic pollutants compared to others under the condition of pH 6.8, applied current of 200 mA, oxidant dosage of 6 mM, and time of 80 min. The oxidation priority was to follow this order: EC/HP > EC/PMS > EC/PDS > EC/PC. These processes enhanced the biodegradability of CWLL based on the average oxidation state and biochemical oxygen demand (BOD)/COD ratio. SUVA254 and E2/E3 indices were also investigated on obtained effluents. The phytotoxicity evaluation was carried out based on the germination index, indicating that the electro-activated oxidant was an effective system to reduce the toxicity of polluted waters. EC/HP showed supremacy compared to others in terms of efficiency, cost, and detoxification. Therefore, the electro-activated oxidant system is a good means for removing organic pollutants from real wastewater.

In-situ electro-generation and activation of hydrogen peroxide using a CuFeNLDH-CNTs modified graphite cathode for degradation of cefazolin.

The modified multifunctional electrodes for electro-Fenton (EF) process are suggested to be promising cathodes for in situ electro-generation and activation of H2O2 to produce hydroxyl radicals (•OH). However, heterogeneous EF process still faces the challenges of limited catalytic activity and releasing of massive amounts of transition metals to the solution after removal of organic pollutants. The main aim of the present investigation was to prepare a cathode containing carbon nanotubes (CNTs) and CuFe nano-layered double hydroxide (NLDH) for degradation and mineralization of cefazolin antibiotic through electro-Fenton process. Structural and electrochemical analyses demonstrated that CuFeNLDH-CNTs nanocomposite was successfully incorporated on the surface of graphite cathode. Due to the increased formation of •OH in the reactor, the incorporation of CNTs into NLDH matrix with a catalyst loading of 0.1 g substantially improved the degradation efficiency of cefazolin (89.9%) in comparison with CNTs-coated (28.7%) and bare graphite cathode (22.8%) within 100 min. In the presence of 15 mM of ethanol, the degradation efficiency of cefazolin was remarkably decreased to 43.7% by the process, indicating the major role of •OH in the destruction of target molecules. Acidic conditions favored the degradation efficiency of cefazolin by the modified EF process. Mineralization efficiency of the bio-refractory compound was obtained to be 70.1% in terms of chemical oxygen demand (COD) analysis after 300 min. The gas chromatography-mass spectroscopy (GC-MS) analysis was also implemented to identify the intermediate byproducts generated during the degradation of cefazolin in the CuFeNLDH-CNTs/EF reactor.

Facile hydrothermal synthesis of novel Fe-Cu layered double hydroxide/biochar nanocomposite with enhanced sonocatalytic activity for degradation of cefazolin sodium.

This study reports the successful synthesis of Fe-Cu layered double hydroxide (Fe-Cu-LDH) /biochar (BC) nanocomposite by a hydrothermal method. The sonocatalytic performance of Fe-Cu-LDH/BC nanocomposite was investigated for the degradation of cefazolin sodium (CFZ), as a model emerging contaminant, from the solution. The physico-chemical properties of the synthesized samples were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDX), Brunauer-Emmett-Teller (BET), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR), and UV-Vis diffuse reflectance spectroscopy (DRS) analyses. The best sonocatalytic efficiency of 97.6% was achieved by using 1.0 g/L sonocatalyst, 0.1 mM CFZ, and an ultrasonic power of 300 W at pH = 6.5 (natural) within 80 min. Additionally, the effects of the addition of various oxidants, dissolved gases, and organic and inorganic scavengers on the degradation of CFZ were studied. Moreover, the possible sonocatalytic mechanism of the sonochemical degradation of CFZ in the presence of Fe-Cu-LDH/BC sonocatalyst was proposed based on the results of GC-MS analysis. The mineralization of CFZ solution was evaluated using COD and IC analyses. Finally, the reusability test of Fe-Cu-LDH/BC nanocomposite in the CFZ degradation revealed that almost 9% drop occurred after five successive cycles.

Sonocatalytic removal of methylene blue from water solution by cobalt ferrite/mesoporous graphitic carbon nitride (CoFe2O4/mpg-C3N4) nanocomposites: response surface methodology approach.

In this study, cobalt ferrite/mesoporous graphitic carbon nitride (CoFe2O4/mpg-C3N4) nanocomposites were successfully synthesized by using a two-step protocol. Firstly, monodispersed CoFe2O4 nanoparticles (NPs) were synthesized via thermal decomposition of metal precursors in a hot surfactant solution and then they were assembled on mpg-C3N4 via a liquid phase self-assembly method. The sonocatalytic performance of as-synthesized CoFe2O4/mpg-C3N4 nanocomposites was evaluated on the methylene blue (MB) removal from water under ultrasonic irradiation. For this purpose, response surface methodology (RSM) based on central composite design (CCD) model was successfully utilized to optimize the MB removal over CoFe2O4/mpg-C3N4 nanocomposites. Analysis of variance (ANOVA) was applied to investigate the significance of the model. The results predicted by the model were obtained to be in reasonable agreement with the experimental data (R2 = 0.969, adjusted R2 = 0.942). Pareto analysis demonstrated that pH of the solution was the most effective parameter on the sonocatalytic removal of MB by CoFe2O4/mpg-C3N4 nanocomposites. The optimum catalyst dose, initial dye concentration, pH, and sonication time were set as 0.25 g L-1, 8 mg L-1, 8, and 45 min, respectively. The high removal efficiency of MB dye (92.81%) was obtained under optimal conditions. The trapping experiments were done by using edetate disodium, tert-butyl alcohol, and benzoquinone. Among the reactive radicals, •OH played a more important role than h+ and [Formula: see text] in the MB dye removal process. Moreover, a proposed mechanism was also presented for the removal of MB in the presence of CoFe2O4/mpg-C3N4 nanocomposites under the optimized sonocatalytic conditions. Finally, a reusability test of the nanocomposites revealed a just 9.6% decrease in their removal efficiency after five consecutive runs.

Sonochemical synthesis of WS2 nanosheets and its application in sonocatalytic removal of organic dyes from water solution.

In this research, tungsten disulfide (WS2) nanosheets as sonocatalyst were synthesized through a sonochemical route. Characterization of as-synthesized sonocatalyst was carried out by X-ray diffraction (XRD), scanning electron microscopy (SEM), electron dispersive X-ray spectroscopy (EDX), Dot-mapping, high resolution transmission electron microscopy (HRTEM), Brunauer-Emmett-Teller (BET), Fourier transform infrared spectroscopy (FTIR), and ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS) analysis. WS2 nanosheets were evaluated for their sonocatalytic performance in order to remove basic violet 10 (BV10) under ultrasonic irradiation. The removal efficiency was maximized (94.01%) via the use of 1 g L-1 catalyst and 10 mg L-1 BV10 at pH = 4.5 and an ultrasonic power of 400 W within a reaction time of 150 min. In addition to BV10, the sonocatalytic elimination for a number of organic dyes viz. direct blue 71, acid blue 92, methylene blue, basic orange 2 and basic red 46 was examined to demonstrate the performance of WS2 nanosheets under the ultrasonic irradiation. The experimentation of trapping was conducted using edetate disodium (EDTA-2Na), tert-butyl alcohol (t-BuOH), and benzoquinone (BQ). According to the results, all radicals participated in the sonocatalytic activity. OH played a more prominent role than h+ and O2-∙ in the process of BV10 separation. Following five repetitive runs, the nanocomposites revealed a reusability of circa 18% drop in the elimination efficiency. The main removal intermediates were recognized by GC-MS technique.

Enhanced removal of basic violet 10 by heterogeneous sono-Fenton process using magnetite nanoparticles.

The removal of basic violet 10 (BV10), which is known as a cationic dye, from aqueous solution was studied by employing a heterogeneous sono-Fenton process over the nano-sized magnetite (Fe3O4) which had been prepared by the milling of magnetite mineral using a high-energy planetary ball milling process. The magnetite samples were characterized using the X-ray diffraction (XRD), high resolution scanning electron microscopy (HR-SEM), energy-dispersive X-ray spectroscopy (EDX), Brunauer-Emmett-Teller (BET), Fourier transform infrared spectroscopy (FTIR), and inductively couple plasma mass spectrometer (ICP-MS). It was found that the catalytic activity of the ball-milled magnetite sample was enhanced along with the improvement in its physicochemical properties; also, the ball-milled magnetite of 6 h displayed the highest catalytic activity in BV10 removal by the heterogeneous sono-Fenton process as compared with that for 4 h (66.12% after 120 min) and 2 h (48% after 120 min).The effect of operational parameters, namely, pH solution, catalyst dosage, the initial H2O2 concentration, ultrasonic power and the initial BV10 concentration, on the removal efficiency (RE%) of BV10 was investigated. The optimum conditions for the BV10 RE% were: the pH value of 3, the catalyst dosage of 1.5 g L-1, the initial H2O2 concentration of 36 mM, the ultrasonic power of 450 W L-1, and the initial BV10 concentration of 30 mg L-1. The RE% of BV10 was 75.94% at these conditions after the reaction time of 120 min. The trapping experiments revealed that OH radicals were the dominant oxidative species, but O2-/HO2 radicals also had a partial role in the removal of BV10.The reusability of the magnetite nanoparticles revealed about 28% decrease in the removal efficiency within five consecutive runs. The results obtained through GC-MS analysis also confirmed the efficient removal of BV10 molecules in the aqueous solution during the process.

Preparation of magnetite nanoparticles by high-energy planetary ball mill and its application for ciprofloxacin degradation through heterogeneous Fenton process.

In this study, the heterogeneous Fenton oxidation of ciprofloxacin (CIP) in an aqueous solution was examined over the nano-sized magnetite (Fe3O4) as a catalyst supplied through high-energy planetary ball milling process. To characterize the magnetite samples after and before ball milling operation, the X-ray diffraction (XRD), High-resolution scanning electron microscopy (HR-SEM), energy-dispersive X-ray spectroscopy (EDX), Brunauer-Emmett-Teller (BET) and Fourier transform infrared spectroscopy (FTIR) analysis were applied. The catalytic properties of the magnetite were considerably improved because of the enhancement in its physical properties, resulted from milling process. The findings also indicated that 6 h ball-milled magnetite demonstrated better properties for elimination of CIP of about 89% following 120 min reaction at optimal conditions of H2O2 12 mM, Fe3O4 1.75 g L-1, CIP 10 mg L-1 and pH 3.0. The effects of various operational parameters, including the initial pH of the solution, H2O2 initial concentration, catalyst dosage, milling time and CIP initial concentration was investigated. Application of organic and inorganic scavengers considerably decreased the CIP removal efficiency. Correspondingly, with respect to the leached iron values at pH 3, it was concluded that CIP elimination was mainly occurred through heterogeneous Fenton procedure. This process included the adsorption and oxidation phases in which the hydroxyl radicals (OH) played a significant role. GC-MS analysis was used for recording of the generated intermediates of the CIP removal in the course of heterogeneous Fenton process.

Heterogeneous sono-Fenton-like process using magnetic cobalt ferrite-reduced graphene oxide (CoFe2O4-rGO) nanocomposite for the removal of organic dyes from aqueous solution.

We report herein the synthesis of monodisperse cobalt ferrite (CoFe2O4) nanoparticles (NPs) via a surfactant-assisted high temperature thermal decomposition method and then their assembly on reduced graphene oxide (rGO) to yield CoFe2O4-rGO nanocomposites, which displayed outstanding sonocatalytic activity for the removal of organic dyes from aqueous solutions under ultrasonic irradiation. As-prepared CoFe2O4-rGO nanocomposites were characterized by using transmission electron microscopy (TEM), high-resolution scanning electron microscopy (HR-SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Micro-Raman spectroscopy, Vibrating sample magnetometer (VSM) and inductively couple plasma mass spectrometer (ICP-MS). To evaluate the sonocatalytic activity of the CoFe2O4-rGO nanocomposites, the sonocatalytic removal of several organic dyes (AO7, AR17, BR46 and BY28) was studied. The reaction conditions were optimized by studying the effects of various key operating parameters such as pH, catalyst dosage, H2O2 initial concentration, initial dye concentration, ultrasonic power and reaction time on the removal of AO7 dye. The maximum removal efficiency of 90.5% was achieved at pH 3 using 0.08gL-1 catalyst, 3mM H2O2 and 10mgL-1 AO7 dye under 350W ultrasonic power in 120min of reaction time span. Experimental results revealed that the kinetic of the removal process could be described using Langmuir-Hinshelwood (L-H) kinetic model. The trapping experiments showed that O2·- radicals constitute the major reactive oxygen species (ROS) in the AO7 dye removal process. The reusability of the nanocomposites revealed about 22% drop in the removal efficiency within five consecutive runs. A possible sonocatalytic mechanism for the removal of organic dyes was also proposed. The intermediate by-products of the dye formed in the removal process were characterized by using the GC-MS technique.

Sonocatalytic degradation of ciprofloxacin using synthesized TiO2 nanoparticles on montmorillonite.

TiO2/Montmorillonite (TiO2/MMT) nanocomposite as sonocatalyst was produced by immobilizing synthesized TiO2 on the surface of montmorillonite. The characteristics of produced nanocomposite were investigated using XRD, XRF, FTIR, TEM, SEM, EDX, UV-vis DRS and nitrogen adsorption-desorption analyses. The synthesized TiO2 and TiO2/MMT samples were applied as catalysts for sonocatalytic degradation of ciprofloxacin (CIP). The performance of the TiO2/MMT was greater than pure TiO2 sample in treatment of CIP solution. The degradation efficiency of the CIP by sonocatalytic process was affected by solution pH, catalyst dosage, initial CIP concentrations and ultrasonic power. Degradation efficiency of 65.01% was obtained at the pH of 6, catalyst dosage of 0.2gL-1, initial CIP concentration of 10mgL-1 and ultrasonic power of 650WL-1. It was observed that the presence of inorganic and organic scavengers suppressed the performance of sonocatalytic process. The stability of the nanocomposite was studied in several successive experiments, and the degradation efficiency declined only 61.48% after 4 repeated experiments. The main degradation by-products were recognized by GC-MS method to propose the possible sonocatalytic mechanism for the degradation of CIP.

Surfactant-modified montmorillonite as a nanosized adsorbent for removal of an insecticide: kinetic and isotherm studies.

Surfactant-modified montmorillonites (MMT) were prepared using trimethyloctylammonium bromide (TMOAB) and employed as a nanosized adsorbent to remove diazinon from aqueous solutions. The prepared adsorbent was characterized using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX). The dependence of removal efficiency on initial diazinon concentration, amount of adsorbent, pH of the solution and ionic strength was investigated. The affinity sequence for ion adsorption on TMOAB/MMT was in the order: without anion> sodium carbonate> sodium bicarbonate> sodium sulphate> sodium chloride. The adsorption kinetic and isotherm were best fit by a pseudo-second-order kinetic and Langmuir isotherm models, respectively.

Sonocatalytic removal of an organic dye using TiO2/Montmorillonite nanocomposite.

The sonocatalytic performance of the synthesized TiO2/Montmorillonite K10 (TiO2/MMT) nanocomposite was studied in removal of Basic Blue 3 (BB3) from water. The TiO2/MMT nanocomposite was prepared by hydrothermal method. Scanning electron microscope, X-ray diffraction and Fourier transform infrared were used to characterize the synthesized nanocomposite. The average size of TiO2 nanoparticles decreased from 60-80nm to 40-60nm through the immobilization of this semiconductor on the surface of MMT. The obtained results indicated that the sonocatalytic activity of TiO2/MMT nanocomposite was higher than that of pure TiO2 nanoparticles and MMT particles. Furthermore, the main influence factors on the sonocatalytic activity such as the BB3 concentration, pH of solution, TiO2/MMT dose, power of ultrasonic generator, and inorganic salts were studied. The intermediates of BB3 degradation during the sonocatalytic process in the presence of the TiO2/MMT nanocomposite have been monitored by gas chromatography-mass spectrometry.