Pre-treatment of real pharmaceutical wastewater by heterogeneous Fenton and persulfate oxidation processes.

This study compares the pre-oxidation of pharmaceutical wastewater by hydroxyl radical based advanced oxidation (HR-AOP) and a sulfate radical based advanced oxidation process (SR-AOP). The heterogeneous Fenton process is chosen as a model HR-AOP and persulfate (PS) activation as a model SR-AOP. The pre-treatment efficacy of both processes in terms of TOC, and COD removals using Fe3O4-rGO catalyst were considered. Under the investigated experimental conditions, both processes yielded fluctuating COD values with time. The heterogeneous Fenton process discovered to be the most efficient to remove 68.7% TOC in 180 min of treatment, when Fe3O4-rGO: H2O2 = 300 mg L-1:150 mM H2O2 was used at pH 3. Notably, the heterogeneous Fenton system was not considerably inhibited at the natural pH of pharmaceutical wastewater (6.75), as the process successfully removed 64.6% TOC. On the other hand, in persulfate activation studies, Fe3O4-rGO: PS = 400 mg L-1: 5 mM was the ideal condition for removing 59.5% TOC in 180 min at pH 3. Whereas the natural pH condition significantly inhibited the TOC removal, as only 20.8% TOC removal was feasible. The wastewater characterisation before and after Fenton treatment reveals that Fenton oxidation leads to an increase in inorganics (chlorides: 160 ± 15 mg L-1, nitrates: 63.14 ± 3.08 mg L-1, sulfates: 266.31 ± 31.39 mg L-1) necessitating an additional treatment step to reduce COD and inorganics further.

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.

Applications of biochar in sulfate radical-based advanced oxidation processes for the removal of pharmaceuticals and personal care products.

Recently, biochar (BC) has been increasingly used as a catalyst for the degradation of 'emerging pollutants' (EPs). Pharmaceuticals and personal care products (PPCPs), which come under 'EPs', can be harmful to the aquatic ecosystem despite being present in very low concentrations (ng/L-µg/L). Advanced oxidation processes (AOPs), which produce sulfate radical (SR-AOPs), show a great potential to degrade PPCPs effectively from wastewater. It is mainly due to the higher stability, long half-lives and better non-selectivity of SO4• - compared with AOPs with •OH generation. Furthermore, research focus is now given on AOPs coupled with BC-supported catalyst to enhance the degradation of PPCPs because of quicker generation of radicals (•OH, SO4•-) by the activation of persulfate (PS) and peroxymonosulfate (PMS). This article sheds light on the catalytic ability of BC after its physical and chemical modifications such as acid/alkali treatment and metal doping. The role of persistent free radicals (PFRs) in the BC for effective removal of PPCPs has been elaborated. Its potential applications in synthetic as well as real wastewater have also been discussed.

Integrated soil washing and bioreactor systems for the treatment of hexachlorocyclohexane contaminated soil: A review on enhanced degradation mechanisms, and factors affecting soil washing and bioreactor performances.

Investigations about the remediation of Hexachlorocyclohexane (HCH), a persistent organic pollutant of global concern, have been extensively reported to treat the HCH contaminated soil. The difficulty arising due to desorption and long ageing procedures of this hydrophobic organic compound in the soil, make it necessary to exploit techniques like soil washing or addition of surfactants, for enhancing the mass transfer rate of hydrophobic compounds. However, this technique gives rise to the generation of a large quantity of waste solution containing the pollutant and various other toxic substances. Moreover, it is challenging to deal with the complex soil washing solution, and thus a follow-up treatment of such washing solution is essentially required before its discharge. This follow-up treatment could be the bioreactor system to efficiently treat the pollutant in the wash solution, thereby reducing the amount of contaminated soil that has to be treated. Among many suggested remediation methods and treatment technologies, integrated soil washing and post-treatment with the bioreactor system could be an environmentally viable method for the remediation of HCH contaminated sites. This review focuses on the soil washing procedures applied so far for the HCH contaminated soil and various factors affecting the efficiency of separation of the target pollutant. Furthermore, the environmental and reactor design-related factors are also discussed for degradation of HCH in the reactor system. Finally, advantages and environmental feasibility of this proposed combined technology and the challenges that need to be encountered are envisaged.

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.

Synthesis of biochar from iron-free and iron-containing microalgal biomass for the removal of pharmaceuticals from water.

The contamination of natural water bodies with pharmaceutical compounds has raised significant concerns about ecological and public health safety. In this study, biochars were synthesized from iron-free microalgal biomass (harvested by centrifugation) and iron-containing microalgal biomass (harvested by coagulation) and tested for the adsorption of ciprofloxacin (CIP) and diclofenac (DIC) from water in batch and fixed-bed column continuous studies. The physicochemical properties of synthesized biochars were analyzed using Brunauer, Emmett and Teller (BET) surface area analyzer, elemental analyzer, Fourier Transformed Infrared spectroscopy (FTIR), X-ray Diffractometer (XRD), and Scanning electron microscope with energy dispersive spectroscopy (SEM-EDS). The maximum monolayer adsorption capacities of iron-containing biochar (FBC750W) and iron-free biochar (MBC750W) based on the Langmuir model were obtained as 75.97 mg/g and 39.08 mg/g for CIP, and 40.99 mg/g and 6.77 mg/g for DIC, respectively. Comparatively, maximum monolayer adsorption capacities of commercial activated carbon (C-AC) were found to be 50.97 mg/g and 46.39 mg/g for CIP and DIC, respectively. In fixed-bed column continuous adsorption studies, the effects of flow rate (1 and 2 mL/min) and the adsorbent amount (50 and 100 mg) on adsorption performance were evaluated. Column kinetic models, such as Bohart-Adams model and Fractal-like Bohart-Adams model were examined. The adsorption mechanisms were proposed as pore filling, π-π interaction, and electrostatic interaction. Overall, the results of this study revealed that microalgal biomass, harvested with FeCl3, can be used for the direct synthesis of iron-containing biochar for the removal of pharmaceuticals from water.

Conversion of sewage sludge into biochar: A potential resource in water and wastewater treatment.

Production of biochar from sewage sludge (SS) is consistent with the goal of sustainable resource recovery and promotes a wastewater-based circular economy. Thermochemical conversion of SS to biochar resolves two major issues simultaneously as it minimizes the cost of disposal and acts as a resource to eliminate the toxic contaminants from water and wastewater. The reusability and ready availability of the biochar, irrespective of the season, makes it an economically viable material for wastewater treatment. In this review, explicit insights into the production, modification and usage of SS derived biochar are provided including (i) the production yield, (ii) characteristic features such as physical, chemical, electrochemical and morphological aspects, and (iii) impact on contaminant removal through adsorption, catalytic and electrochemical processes. Particular attention is given to the use of SS derived biochar as an adsorbent for contaminants present in wastewaters, the potential use of biochar as a catalyst and support material in advanced oxidation processes and the use of biochars as an electrode material. The effect of pyrolysis conditions and co-pyrolysis with other materials on biochar properties is explored and insight is provided into the toxicity of biochar components present at different process conditions.

Synthesis and applications of various bimetallic nanomaterials in water and wastewater treatment.

Bimetallic nanoparticles are the complex combination of two different metal constituents in nanoscale. Water and wastewater treatment utilizing bimetallic particles is an emerging research area. When two metals are combined, it can show not only the properties of its constituents but also new and enhanced properties derived by the synergy of the combination. These properties of bimetallic nanoparticles inevitably depend on the size, structure, and morphology of the particles. Thus the adopting synthesis strategy is very crucial to achieve desired results. Here in this review, the various bimetallic synthesis strategies are compared. The bimetallic nanoparticles decontaminate water through adsorption and/or catalysis mechanism. The various degradation pathways, specifically, adsorption, reduction, oxidation, and advanced oxidation processes are discussed in detail in this review.

Combined heterogeneous Electro-Fenton and biological process for the treatment of stabilized landfill leachate.

Treatment of stabilized landfill leachate is a great challenge due to its poor biodegradability. Present study made an attempt to treat this wastewater by combining electro-Fenton (E-Fenton) and biological process. E-Fenton treatment was applied prior to biological process to enhance the biodegradability of leachate, which will be beneficial for the subsequent biological process. This study also investigates the efficiency of iron molybdophosphate (FeMoPO) nanoparticles as a heterogeneous catalyst in E-Fenton process. The effects of initial pH, catalyst dosage, applied voltage and electrode spacing on Chemical Oxygen Demand (COD) removal efficiency were analyzed to determine the optimum conditions. Heterogeneous E-Fenton process gave 82% COD removal at pH 2, catalyst dosage of 50 mg/L, voltage 5 V, electrode spacing 3 cm and electrode area 25 cm2. Combined E-Fenton and biological treatment resulted an overall COD removal of 97%, bringing down the final COD to 192 mg/L.

Iron impregnated biochars as heterogeneous Fenton catalyst for the degradation of acid red 1 dye.

In the present work, Acid Red 1 (AR1) dye degradation by two heterogeneous Fenton catalysts, namely iron loaded rice husk biochar (Fe-RHB) and coir pith biochar (Fe-CPB) are studied. Biochar prepared from RHB and CPB were sonicated in the presence of ferric nitrate for the synthesis of Fe-RHB and Fe-CPB by incipient impregnation method. Effect of operational parameters such as pH, the dosage of catalyst, H2O2 concentration and temperature were examined. Characterization of the synthesized Fenton catalyst, Fe-RHB and Fe-CPB were analysed by SEM, EDS, XRD and XPS techniques. In Fe-RHB Fenton system, maximum dye removal efficiency of 97.6% and TOC removal efficiency of 84.2% were obtained at pH 3 for 50 mg L-1 of AR1 concentration, with 16 mM of H2O2 and 5 g L-1 of catalyst dosage within 120 min reaction time. Similarly, for Fe-CPB, maximum dye removal efficiency of 99.1% and TOC removal efficiency of 86.7% were obtained with 16 mM of H2O2 and 4 g L-1 of dosage for 50 mg L-1 of initial dye concentration at pH 3. The prepared catalysts can be reused for successive cycles as the catalyst materials are highly stable and have very less iron leaching property.

Role of biochar in superoxide-dominated dye degradation in catalyst-activated peroxymonosulphate process.

In recent times, the application of biochar (BC) as an upcoming catalyst for the elimination of recalcitrant pollutants has been widely explored. Here, an iron loaded bamboo biochar activated peroxymonosulphate (PMS) process was tested for removing Congo red (CR) dye from water medium. The catalyst was synthesized using a green synthesis method using neem extracts and characterized using SEM, FTIR, and XRD. The effects of various operating parameters, including solution pH, catalyst dosage, and pollutant dosage, on dye degradation efficiency were examined. The results showed that at the optimized conditions of 300 mg L-1 PMS concentration, 200 mg L-1 catalyst dosage, and pH 6, about 89.7% of CR dye (initial concentration 10 ppm) was removed at 60 min of operation. Scavenging experiments revealed the significant contribution of O2•-, •OH, and 1O2 for dye degradation, with a major contribution of O2•-. The activation of PMS was mainly done by biochar rather than iron (loaded on biochar). The catalyst was highly active even after four cycles.

Conversion of locally available materials to biochar and activated carbon for drinking water treatment.

For environmental sustainability and to achieve sustainable development goals (SDGs), drinking water treatment must be done at a reasonable cost with minimal environmental impact. Therefore, treating contaminated drinking water requires materials and approaches that are inexpensive, produced locally, and effortlessly. Hence, locally available materials and their derivatives, such as biochar (BC) and activated carbon (AC) were investigated thoroughly. Several researchers and their findings show that the application of locally accessible materials and their derivatives are capable of the adsorptive removal of organic and inorganic contaminants from drinking water. The application of locally available materials such as lignocellulosic materials/waste and its thermo-chemically derived products, including BC and AC were found effective in the treatment of contaminated drinking water. Thus, this review aims to thoroughly examine the latest developments in the use of locally accessible feedstocks for tailoring BC and AC, as well as their features and applications in the treatment of drinking water. We attempted to explain facts related to the potential mechanisms of BC and AC, such as complexation, co-precipitation, electrostatic interaction, and ion exchange to treat water, thereby achieving a risk-free remediation approach to polluted water. Additionally, this research offers guidance on creating efficient household treatment units based on the health risks associated with customized adsorbents and cost-benefit analyses. Lastly, this review work discusses the current obstacles for using locally accessible materials and their thermo-chemically produced by-products to purify drinking water, as well as the necessity for technological interventions.

Modeling of crystal violet adsorption by bottom ash column.

The removal of crystal violet from wastewater, by means of bottom ash, was investigated in a packed bed down-flow column. The bed depth service time (BDST) model was used to analyze the experimental data up to breakthrough time (corresponding to C(t)/C(0) = 0.1). A mass transfer model was used to analyze the mass transfer zone. The breakthrough curve was analyzed by the Thomas, Yoon-Nelson, and Clark models. All models fit well with the experimental data. Results showed that as the flow rate increases, at a constant concentration and bed depth, the value of the adsorption capacity of bottom ash decreases. The adsorption capacity of bottom ash decreases with an increase in depth and initial crystal violet concentration. Error analyses were performed for the Thomas, Yoon-Nelson, and Clark models. Water

Combination of electrochemically activated persulfate process and electro-coagulation for the treatment of municipal landfill leachate with low biodegradability.

To handle complex wastewater with limited biodegradability, hybrid treatment systems are necessary. The current study represents the combined effectiveness of sulfate-radical associated electro-chemical advanced oxidation process (SR-EAOP) and electro-coagulation (EC) for the treatment of stabilized landfill leachate. For SR-EAOP, Pt/Ti was employed as the anode and an iron plate as the cathode; while EC treatment was performed by switching the polarity. Hence, both electrochemical treatment was carried out in single reactor. Initially, the effects of pH, applied voltage, persulfate and Fe2+ dosage, on the performance of SR-EAOP was examined. Sulfate radical was generated in the electrolytic system via cathodic reduction of persulfate (PS) and ferrous (Fe2+) ion activation. Auxiliary processes such as anodic oxidation via Pt/Ti anode and indirect electro-chemical oxidation were also contributed for pollutant degradation. Combined process SR-EAOP followed by EC (SR-EAOP + EC) has better leachate treatment efficacy in comparison with EC + SR-EAOPs. The SR-EAOP + EC based combined treatment mechanism achieved an efficient COD reduction of 88.67% than that of EC + SR - EAOP process (74.51% COD reduction). Characterization studies have been carried out for post-treated dried-sludge using Field Emission scanning electron microscope (FE-SEM) and X-ray powder diffraction (XRD) techniques. The combined process treatment (SR-EAOP + EC) can be applied as pre-treatment for leachate decontamination.

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.

Recent advancements in peroxicoagulation process: An updated review.

The present article describes the recent advancements (since 2018) in peroxicoagulation (PC) process, which was introduced by Professor Enric Brillas and his group in 1997. Instead of checking the efficiency of PC process to degrade a targeted pollutant in synthetic wastewater, researchers started testing its efficacy for the treatment of complex real wastewater. Applications like disinfection and removal of heavy metals as well as oxidative removal of arsenite from water were tested recently. To improve the efficiency of PC process, modifications were made for electrode materials (both anode and cathode) and electrolytic cells. Performance of PC process in combination with other treatment technologies is also discussed.

Chelate-modified Electro-Fenton process for mixed industrial wastewater treatment.

HIGHLIGHTS: The Chelate-modified EF process for the removal of COD at near neutral pHTreatment of the mixed industrial wastewater with very low BOD/COD ratioInfluence of Fenton catalyst and chelating agent dosage on COD removal.Comparable COD removal of 67% with Chelate-modified EF at near neutral pH and 66% with EF at acidic pH.Mineralization current efficiency and instantaneous current efficiency for COD removal.

Occurrence of organic micropollutants in municipal landfill leachate and its effective treatment by advanced oxidation processes.

Landfilling is the most prominently adopted disposal technique for managing municipal solid waste across the globe. However, the main drawback associated with this method is the generation of leachate from the landfill site. Leachate, a highly concentrated liquid consisting of both organic and inorganic components arises environmental issues as it contaminates the nearby aquifers. Landfill leachate treatment by conventional methods is not preferred as the treatment methods are not much effective to remove these pollutants. Advanced oxidation processes (AOPs) based on both hydroxyl and sulfate radicals could be a promising method to remove the micropollutants completely or convert them to non-toxic compounds. The current review focuses on the occurrence of micropollutants in landfill leachate, their detection methods and removal from landfill leachate using AOPs. Pharmaceuticals and personal care products occur in the range of 10-1 to more than 100 µg L-1 whereas phthalates were found below the detectable limit to 384 µg L-1, pesticides in the order of 10-1 µg L-1 and polyaromatic hydrocarbons occur in concentration from 10-2 to 114.7 µg L-1. Solid-phase extraction is the most preferred method for extracting micropollutants from leachate and liquid chromatography (LC) - mass spectrophotometer (MS) for detecting the micropollutants. Limited studies have been focused on AOPs as a potential method for the degradation of micropollutants in landfill leachate. The potential of Fenton based techniques, electrochemical AOPs and ozonation are investigated for the removal of micropollutants from leachate whereas the applicability of photocatalysis for the removal of a wide variety of micropollutants from leachate needs in-depth studies.

Effective degradation of azo dye from textile wastewater by electro-peroxone process.

Color-producing chemicals emitted from many sources, such as textile or dye manufacturing industries, are a significant concern worldwide. The present study focuses on the electro-peroxone (EP) process for decolorizing a synthetic azo dye, C.I. Reactive Black 5 (RB5). Findings suggest that the EP process is more effective for dye degradation than ozonation and electrolysis. The EP process resulted in 100% decolorization after 60 min of contact time under optimum testing conditions such as pH 7, applied current 300 mA, and sulfate concentration 3.55 g L-1. Based on the findings of the primary investigation, EP treatment of real textile effluent was carried out and 2 h of EP treatment resulted in 99% decolorization and 74%total organic carbon (TOC) removal. As an outcome, the EP process can treat textile wastewater in a cost-effective and environmentally friendly manner.