Highest Total Organic Carbon Removal Research Articles

Ingenious development of bandgap engineered MIL-101(Fe) core-shell supported on SnO2/ZnO heterojunction and its photocatalytic activity towards azo dye degradation: Process optimization and mechanistic insight

Water pollution is a pressing global concern, exacerbated by industrial effluents containing hazardous azo-dyes such as Trypan blue (TB) and Methyl orange (MO), which contaminate water bodies and threaten ecosystems. The scarcity of pure water intensifies the urgency to develop effective remediation strategies to tackle the toxic dye pollutants. In the present work, an attempt has been made to fabricate and utilize a novel ternary MOF-based SnO2/ZnO@MIL-101(Fe) photocatalyst for the removal of TB and MO dyes from an aqueous medium. The photocatalyst was characterized using various analytical techniques, like XRD, FTIR, UV–vis DRS, PL, SEM, TEM, and XPS, which provide insights into the composites’ crystal structure, morphology, and optical properties, which are crucial for understanding their photocatalytic behavior. The photocatalytic performance of the heterojunction was investigated under various reaction parameters such as catalyst dosage, initial concentration of dyes, and light irradiation time. The results demonstrated the superior performance of the SnO2/ZnO@MIL-101(Fe) composites in degrading the mono-azo and di-azo dyes under visible light irradiation via a photo-fenton process. The maximum degradation efficiency of 97.44 % and 98.8 % were obtained for TB and MO within 30 and 55 min, respectively. Furthermore, the change in the total organic carbon (TOC) was monitored to verify the degree of mineralization of the azo dyes. The extremely high dye degradation activity and TOC removal can be attributed to the formation of a suitable heterojunction interface between the components of the photocatalyst, leading to effective charge carrier transport and the generation of active radicals. Finally, based on the radical scavenging experiments, ESR, and VB-XPS analysis, a plausible mechanism for the photodegradation process was derived. This research contributes to the advancement of sustainable water treatment technologies by providing insights into the design, fabrication, and utilization of novel composites for efficient remediation of dye-contaminated wastewater.

Magnetic composite photocatalyst NiFe₂O₄/ZnIn₂S₄/biochar for efficient removal of antibiotics in water under visible light: Performance, mechanism and pathway

The widespread presence of antibiotics in aquatic environments, resulting from excessive use and accumulation, has raised significant concerns. A NiFe₂O₄/ZnIn₂S₄/Biochar (NFO/ZIS/BC) magnetic nanocomposite was successfully synthesized, demonstrating significantly enhanced electron-hole separation properties. Comprehensive investigations were conducted to evaluate the impact of various parameters, including catalyst mass, pH, and the presence of co-existing ions on the composite's performance. The nanoparticles of NiFe₂O₄ (NFO) and ZnIn₂S₄ (ZIS) were found to improve the surface stability and sulfamethoxazole removal capabilities of porous biochar, while also demonstrating high total organic carbon removal efficiencies. •O₂⁻ and h⁺ were identified as the predominant reactive oxygen species (ROS) in NFO/ZIS/BC-4 during the degradation process. The degradation outcomes of sulfamethoxazole under natural sunlight and water conditions were consistent with laboratory findings, affirming the robust applicative potential of NFO/ZIS/BC. Density functional theory (DFT) calculations were performed to elucidate the photocatalytic mechanism and identify potential intermediate products. Additionally, the types of heterojunctions present in the system were characterized and discussed. After multiple iterations, NFO/ZIS/BC-4 maintained effective photodegradation capabilities through five cycles. This study presents an effective method for the treatment of antibiotics in aquatic environments, offering significant potential for environmental applications.

A Novel Process for the On-Site Preparation and Application of Polyferric Chloride (PFC) for Surface Water Treatment

This is the first study to describe a novel, patented process for the on-site synthesis and subsequent direct utilisation of Polyferric Chloride (PFC) at low Fe concentration dosing, which aims to facilitate the potential replacement of Polyaluminium Chloride (PAC) during surface water treatment (e.g., from reservoirs) for drinking water production. For this purpose, the PFC was synthesised and subsequently used as a coagulant in simulated surface water samples under different synthesis and coagulation/flocculation conditions, namely for different pre-hydrolysed Fe concentrations, pre-hydrolysis pH, coagulation pH, and flocculation times. The effectiveness of PFC was examined mainly in terms of total organic carbon (TOC) removal and the residual Fe concentration. The obtained results showed that the pre-hydrolysed Fe concentration at 0.5 ± 0.25%, pre-hydrolysis at pH 2.5 ± 0.25, coagulation at pH 5.5–7.0 and a flocculation time of 5 min could result in the highest TOC removal (i.e., residual values < 0.60 mg/L) and the lowest residual Fe concentration (<5 μg Fe/L), which is acceptable for a water quality assessment. These values are also substantially lower when compared to the respective TOC and residual metal concentrations using PAC (usually, the relevant obtained values are around TOC > 1 mg/L and Al > 50 μg/L).

Insights on dielectric barrier discharge plasma treatment of oil drilling cuttings

Oil drilling cuttings produced during oil exploration and extraction contain a high percentage of crude oil, ranging from 5% to 20% weight ratio (w/w) on a dry basis, and must be managed and treated properly before their release to the environment. In this study, non-thermal plasma (NTP) was investigated as an advanced oxidation process for the efficient, sustainable and cost-effective treatment of oil drilling cuttings. To this end, a plane-to-grid dielectric barrier discharge (DBD) reactor operating at atmospheric pressure was tested under different plasma conditions. The effect of treatment time, DBD power and air flow rate on the total organic carbon (TOC) removal efficiency was assessed and the energy efficiency of the process was determined. Within 10 min of plasma treatment, a very high TOC and total petroleum hydrocarbons (TPH) removal (∼90% and ∼99%, respectively) was achieved, while polycyclic aromatic hydrocarbons (PAHs) were degraded by ∼50% within 2 min of treatment. Depending on the experimental conditions, the energy efficiency of the process varied from 5 to 35 mg/kJ. From GC-MS analysis, several byproducts of the oxidation of oil drilling cuttings were identified, while the analysis of exhaust gases revealed that ∼85.1% of the removed organics from oil drilling cuttings was transformed to CO2 and CO. This study provides critical information on the effectiveness of the NTP process for the treatment of heavily contaminated solid wastes and can be considered as the critical step for its application for the treatment of solid wastes from the oil industry.

UV/persulfate processes for the removal of total organic carbon from coagulation-treated industrial wastewaters

Sulfate radical-based oxidation processes were investigated to understand the relationship between persulfate (PS) consumption and total organic carbon (TOC) removal from industrial wastewater under various PS concentrations. First, the degradation and mineralization of Bisphenol A (BPA) (initial concentration: 11 mg/L) were investigated in ultraviolet (UV)/PS systems. Complete degradation was achieved within 30 min of UV irradiation, and 41%–72% TOC removal was achieved at PS concentrations of 200 and 400 mg/L. The consumed concentration of S2O82− and generated concentration of SO42− increased gradually to similar levels. The ratio of the PS consumption to TOC removal based on the mass concentration (mg/L) was 14.5 and 23.2 at 180 min for 200 and 400 mg/L of S2O82−, respectively. Three types of coagulation-treated industrial wastewater from metal-processing, food-processing, and adhesive-producing plants were obtained, and TOC removal was analyzed using the same UV/PS systems (initial TOC concentration: 100 mg/L). The TOC removal rates ranged from 16.9% to 94.4% after 180 min of UV irradiation at PS concentrations of 1,000, 2,000, 4,000, and 8,000 mg S2O82−/L. Despite the higher TOC removal at higher PS concentrations, the PS activation efficiency decreased significantly as the PS concentration increased. Only approximately 30%–40% activation efficiency was achieved at a PS concentration of 8,000 mg/L. In this study, the ratio of PS consumption to TOC removal ranged from 20.6 to 43.9.

Insight into disparate nonradical mechanisms of peroxymonosulfate and peroxydisulfate activation by N-doped oxygen-rich biochar: Unraveling the role of active sites

In this study, we first comprehensively studied peroxymonosulfate (PMS) and peroxydisulfate (PDS) activation mechanisms using N, O codoped sludge biochar (NOSB) to degrade organics from water. Among the catalysts, NOSB with a higher content of graphitic N, optimal edge nitrogen (pyridinic N and pyrrolic N), CO groups, sp2-hybridized C, and rich defects were demonstrated to be a superior catalyst. Therefore, by activating PDS and PMS, NOSB exhibited the highest rate of BPA degradation, which was 22-fold and 13-fold that of pristine sludge biochar, respectively. However, owing to different oxidation potentials and molecular structures, PMS and PDS show different degradation performances due to various catalytic mechanisms occurring, even with the same biochar. Due to the asymmetrical structure of PMS, electrons passed from PMS to NOSB and further generated singlet oxygen (1O2), which governs the degradation of bisphenol A with an auxiliary contribution of single electron transfer. Meanwhile, PDS is reduced at the Lewis basic sites of NOSB, forming inner-surface-bound {PDS-NOSB}, which was oxidizing around neighboring carbon and decomposed targets through transferring single and double electrons. NOSB is promising for practical applications because of its adaptation to a wide pH range, anions, high total organic carbon removal, tunable active sites, and re-usability for degrading organics via PMS/PDS activation. This study unveils knowledge about N, O codoped sludge biochar catalysts for activating PMS/PDS and advocates a great approach for organics’ degradation in the environment.

Application of Ti-based mixed metal oxide electrodes towards electrochemical mineralization of Metronidazole: Evaluation of influencing factors and removal by-products

BackgroundThe treatment of Metronidazole (MTZ) as a persistent pharmaceutical waste in the water is a significant challenge. To reduce the adverse effect of MTZ in water, we tested a novel SiO2-incorporated MMO-Ti/IrO2-Ta2O5 electrode via the electrochemical oxidation (EO) method. MethodsThe electrode was characterized by scanning electron microscopy, energy dispersive spectrum, atomic force microscopy, and cyclic voltammetry analyses. Structural characterization results were represented high resistance, compact surface, and better electrocatalytic properties for Ti/IrO2-Ta2O5-SiO2 electrode. The influence of critical operational parameters, including applied current density, initial pH, initial concentration of MTZ, and electrolysis time, was detected on electrocatalytic removal efficiency. Significant findingsIt was recognized that the high electrocatalytic power of SiO2-incorporated MMO-Ti/IrO2-Ta2O5 electrode gives a high amount of •OH during the removal process. At optimum conditions (pH = 7, J = 200 mA/cm2, [MTZ]0 = 40 mg/L, t = 80 min), 98.76% MTZ removal efficiency was achieved. Besides, comparison analysis was performed with SiO2-incorporated MMO-Ti/IrO2-Ta2O5 electrode and Ti/IrO2-Ta2O5, so results point out the higher total organic carbon removal of about 78.90% and 54.30% with SiO2-incorporated MMO-Ti/IrO2-Ta2O5 than Ti/IrO2-Ta2O5, respectively. Furthermore, MTZ removal intermediates formed during the electrocatalytic oxidation process were identified by the gas chromatography–mass spectrometry technique.

Spherical activated carbons derived from resin-microspheres for the adsorption of acetic acid

Separation of small-molecule carboxylic acids, especially acetic acid, from wastewater is challenging due to its high-water solubility, acidity, and low concentration. In this work, resin-derived spherical activated carbon (RSAC) was directly prepared from resin spheres through facile pre-oxidation and carbonization processes. RSAC was characterized by SEM, N2 physisorption, XRD, Raman, element analysis and XPS. RSAC showed high removal rates (> 95.8 %) for a variety of small-molecule carboxylic acids. The initial adsorption capacity of acetic acid over RSAC was 23.4 mg/g and 94 % of the removal rate was retained after five successive adsorption-desorption cycles for 1000 mg/L acetic acid. In addition, RSAC showed a high total organic carbon removal rate (> 80 %) for the high-salinity effluent of catalytic wet air oxidation (CWAO) process. The adsorption of acetic acid over RSAC complied with the pseudo-second-order model and Langmuir model ideally, through Vander Waals force and pore-filling effect. Furtherly, discarded resin microspheres were used to prepare spherical active carbon, which showed 88.2 % removal of acetic acid (1000 mg/L). The benign scheme of “treating wastes by wastes” from economical and environmental aspects was realized.

Photocatalytic Activity and Reusability of F, Sm3+ Co-Doped TiO2/MWCNTs Hybrid Heterostructure for Efficient Photocatalytic Degradation of Brilliant Black Bis-Azo Dye

A global freshwater pollution catastrophe is looming due to pollutants of emerging concern (PECs). Conventional water treatment methods are limited in removing PECs such as pharmaceuticals and dye house effluent from aquatic systems. This study provides an effective potential solution by developing an innovative wastewater treatment method based on solar-light-responsive semiconductor-based photocatalysts. A sol-gel synthesis technique was used to produce Fluorine-Sm3+ co-doped TiO2 (0.6% Sm3+) (FST3) photocatalysts. This was followed by loading multi-walled carbon nanotubes (MWCNTs) in the range of 0.25 to 1 wt% into the FST3 matrix. Solid state UV-visible spectroscopy measurements showed a bathochromic shift into the visible light region after the co-doping of TiO2, whereas XRD analysis confirmed the presence of predominantly anatase polymorphs of TiO2. The FT-IR and EDX results confirmed the presence of the F and Sm3+ dopants in the synthesised photocatalysts. XRD and TEM measurements confirmed that the crystallite sizes of all synthesised photocatalysts ranged from 12–19 nm. The resultant photocatalysts were evaluated for photocatalytic degradation of Brilliant Black BN bis-azo dye in aqueous solution under simulated solar irradiation. FST3 completely degraded the dye after 3 h, with a high apparent rate constant (Ka) value (2.73 × 10−2 min−1). The degree of mineralisation was evaluated using the total organic carbon (TOC) technique, which revealed high TOC removal (82%) after 3 h and complete TOC removal after 4 h. The incorporation of F improved the optical properties and the surface chemistry of TiO2, whereas Sm3+ improved the quantum efficiency and the optical properties. These synergistic effects led to significantly improved photocatalytic efficiency. Furthermore, incorporating MWCNTs into the F and Sm3+ co-doped TiO2 (0.6% Sm3+) improved the reaction kinetics of the FST3, effectively reducing the reaction time by over 30%. Recyclability studies showed that after 5 cycles of use, the FST3/C1 degradation efficiency dropped by 7.1%, whereas TiO2 degradation efficiency dropped by 33.4% after the same number of cycles. Overall, this work demonstrates a sustainable and efficient dye-removal technique.

Understanding the catalytic ozonation process on ceria nanorods: Efficacy, Frenkel-type oxygen vacancy as a key descriptor and mechanism insight

This work investigated property-activity correlations of ceria (CeO2) in heterogeneous catalytic ozonation (HCO) and explored the key descriptor from various properties. CeO2 nanorods (NRs) calcined at 300–700 °C were adopted in HCO for degrading three organic pollutants. With their physicochemical properties characterized and their HCO performances analyzed in detail, the correlations between different properties and the rates of O3 decomposition, pollutant degradation and total organic carbon (TOC) removal were revealed. Fast pollutant degradation, high TOC removal, good stability and wide pH applicability were achieved. Linear relationships between the rates of O3 decomposition/TOC removal and the density of Frenkel-type oxygen vacancy (OV) were established. Theoretical and spectroscopic studies revealed OV could boost O3 decomposition to generate reactive oxygen species (ROS). The mechanism for ROS generation and pollutant degradation was proposed. This study would contribute to designing efficient catalysts and understanding their performances in HCO for abatement of organic pollutants in wastewaters.

Degradation of phenol by ball-milled activated carbon (ACBM) activated dual oxidant (persulfate/calcium peroxide) system: Effect of preadsorption and sequential injection

This study explored pre-adsorption and sequential injection of dual oxidant (DuOx) of persulfate (PS) and calcium peroxide (CP) for phenol degradation in an aqueous solution. Ball-milled activated carbon (ACBM) was used as the catalyst in the following systems: pre-adsorption and sequential injection of PS and CP (ACBM + PS + CP), pre-adsorption and simultaneous injection of PS and CP (ACBM + PS/CP), simultaneous injection of ACBM, PS, and CP (ACBM/PS/CP), simultaneous injection of ACBM and PS (ACBM/PS), and simultaneous injection of ACBM and CP (ACBM/CP). The ACBM had a larger specific surface area, more graphitic structures, and more defects. Moreover, it showed better phenol removal when introduced simultaneously with PS and CP. The phenol removal was most the efficient in ACBM + PS + CP (98.8%) with a near-neutral final pH, followed by ACBM + PS/CP, ACBM/PS, ACBM/PS/CP, and ACBM/CP. This indicates that pre-adsorption and separate injection of PS and CP were the key strategy for improved performance and maintained favorable pH for the activation of PS and CP. The dual oxidant system (PS/CP) is superior to single oxidant systems (PS or CP). Scavenger experiments and the electron spin resonance spectra (ESR) demonstrated that non-radical species (1O2) were dominantly involved in ACBM + PS + CP, but radical species (HO•, SO4•−) also contributed. HCO3− and HPO42− inhibited phenol degradation in ACBM + PS + CP, whereas Cl− and HA had negligible effects. The ACBM + PS + CP showed high total organic carbon removal and ACBM was recyclable with a slight decrease in activity. This work is important as it provides a detailed insight into the strategy of pre-adsorption and sequential injection of dual oxidants for a practical and cost-effective method of groundwater remediation.

Perfluorooctanoic acid (PFOA) removal from real landfill leachate wastewater and simulated soil leachate by electrochemical oxidation process

Poly and perfluoroalkyl compounds (PFASs) are a group of chemicals that are widely used and are difficult to purify. Within this group, perfluorooctanoic acid (PFOA), known for its highly polar and strong carbon–fluorine bonds, is a frequently encountered species in surface water, drinking water, and groundwater. In this study, we investigated the efficiency of electrooxidation (EO) in PFOA removal, optimization of EO parameters, and groundwater simulation in a realistic scenario. The EO optimization experiments were performed with a boron-doped diamond (BDD) anode for different values of pH, current density, and inlet concentration, and the effects of different anode materials were investigated for comparison. Under optimum conditions, total organic carbon (TOC) removal of up to 90% was achieved. In the groundwater simulation, we applied optimized EO parameters after obtaining leachates from the soil. A TOC removal of up to 86% was obtained in the EO of simulated groundwater contaminated with PFOA. In the case of realistic leachate simulation, four different leachate treatments were applied to PFOA-contaminated soil, and high TOC removal was achieved in all matrices. Additionally, the EO with BDD was applied to landfill leachate wastewater supplemented with PFOA to monitor the effectiveness of the process. A TOC removal of 85% was achieved, and it was observed that the number of free F-ions increased. The results showed that the BDD EO has a high potential for the treatment of PFOA-contaminated groundwater. • A realistic simulation was designed to obtain PFOA-contaminated groundwater. • Parameter optimization for BDD EO was performed. • The effects of different anodes (DSA) in the EO was investigated. • TOC removal efficiencies for water and wastewater were 90% and 78%, respectively. • TOC removal of 85% was achieved for PFOA contaminated groundwater.

A double Z‐scheme catalyst BiOI/g‐C3N4/Bi2WO6 for enhanced photocatalytic activity

AbstractBACKGROUNDTo enhance photocatalyst activity, a Z‐scheme ternary heterojunction of g‐C3N4 and BiOI co‐modified with Bi2WO6 (BiOI/g‐C3N4/Bi2WO6 (BCB)) was prepared. The double Z‐scheme catalyst is advantageous but not well studied for compositing low‐cost g‐C3N4 with Bi‐containing components such as BiOI and Bi2WO6.RESULTSFor g‐C3N4 and BiOI, we determined the optimal doping ratios of 3 wt% BiOI/10 wt% g‐C3N4 /Bi2WO6. It catalyzed almost complete degradation of (100 mg L−1) rhodamine B (RhB) under visible light irradiation (95% in 20 min and 100% in 30 min), with a significant reaction kinetic constant of 0.245 min−1. The remaining high total organic carbon removal rate of RhB, even after five cycles of the experiment, and the good removal effect for different concentrations of tetracycline (TC) proved the effectiveness of the catalyst.CONCLUSIONThe e−, h+, and ·OH, ·O2− reactive species work together, leading to rapid pollutant degradation. The developed triple‐component double Z‐scheme heterojunction catalyst has promising applications in pollution control. © 2022 Society of Chemical Industry (SCI).

Development of High Flux Nanocomposite Polyphenylsulfone/Oxidized Multiwalled Carbon Nanotubes Membranes for Ultrafiltration Using the Systems with Critical Solution Temperatures.

The study deals with the investigation of the effect of the modification of polyphenylsulfone (PPSU) flat sheet membranes for ultrafiltration using oxidized multiwalled carbon nanotubes (O-MWCNT) in order to enhance membrane permeability and antifouling performance. The effect of O-MWCNT loading to the PPSU-polyethylene glycol (PEG-20,000, Mn = 20,000 g·mol−1)-polyvinylpyrrolidone (PVP K-30, Mn = 40,000 g·mol−1)-N-methy-2-pyrrolidinone (NMP) colloid systems on the phase state and viscosity was studied. It was found that PPSU-PEG-20,000-PVP K-30-O-MWCNT-NMP colloid systems feature a gel point (T = 35–37 °C) and demixing temperature (T = 127–129 °C) at which two bulk phases are formed and a polymer system delaminates. According to the study of the phase state and viscosity of these colloid systems, a method for the preparation of high flux PPSU membranes is proposed which includes processing of the casting solution at the temperature higher than gel point (40 °C) and using a coagulation bath temperature lower than gel point (25 °C) or lower than demixing temperature (40 °C and 70 °C). Membrane structure, topology and hydrophilic-hydrophobic balance were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM) and water contact angle measurements. The effect of coagulation bath temperature and O-MWCNT concentration on the membrane separation and antifouling performance in ultrafiltration of human serum albumin and humic acids solutions was studied. It was found that the modification of PPSU ultrafiltration membranes by O-MWCNTs yielded the formation of a thinner selective layer and hydrophilization of the membrane surface (water contact angle decreased from 53–56° for the reference PPSU membrane down to 33° for the nanocomposite membrane with the addition of 0.19 wt.% O-MWCNT). These changes resulted in the increase in membrane flux (from 203–605 L·m−2·h−1 at transmembrane pressure of 0.1 MPa for the reference membrane up to 512–983 L·m−2·h−1 for nanocomposite membrane with the addition of 0.19 wt.% O-MWCNT depending on coagulation bath temperature) which significantly surpasses the performance of PPSU ultrafiltration membranes reported to date while maintaining a high level of human serum albumin rejection (83–92%). It was revealed that nanocomposite membrane demonstrated better antifouling performance (the flux recovery ratio increased from 47% for the reference PPSU membrane up to 62% for the nanocomposite membrane) and higher total organic carbon removal compared to the reference PPSU membrane in humic acids solution ultrafiltration.

Two novel and efficient plant composites for the degradation of oxytetracycline: nanoscale ferrous sulphide supported on rape straw waste.

As a biomass waste, rape straw shows a good application prospect in heterogeneous catalyst preparation due to its low-cost and stable structure. In this study, FeS-modified rape straw (RS-FeS) and its biochar (RSBC-FeS) were firstly synthesized to remove oxytetracycline (OTC). The highest OTC removal capacities observed for RS-FeS and RSBC-FeS were 635.66 and 827.80mgg-1. When compared with the adsorption process, the degradation ratios of the total OTC removal capacity observed in the RS-FeS/H2O2 and RSBC-FeS/H2O2 systems were 70.14 and 79.35%. Degradation was the dominant process observed during the removal of OTC. Both radical (SO4•-, •OH, and O2•-) and non-radical (1O2 and Ov) pathways were involved in the degradation process. OTC was degraded into smaller molecules via hydroxylation, dehydration, quinonization, demethylation, decarbonylation, alcohol oxidation, and ring cleavage reaction, indicating two catalysts could efficiently mineralize organic pollutants. The highest total organic carbon removal efficiencies of observed for RS-FeS and RSBC-FeS in swine wastewater were 88.93 and 96.81%, respectively. In addition, OTC removal efficiency of RS-FeS was more than 80% in successive experiments, further suggesting the feasibility of rape straw to Fenton-like catalysts. In this study, FeS nanoparticles were directly loaded on rape straw for the first time. Compared with biochar, FeS-modified rape straw can also degrade OTC efficiently, which provides an eco-friendly, high-efficient, and sustainable strategy for the preparation of catalyst.

Insights into the generation of hydroxyl radicals from H2O2 decomposition by the combination of Fe2+ and chloranilic acid

In this work, the degradation of chloranilic acid (CAA) by chemical oxidation with H2O2 alone and in the presence of ferrous iron Fe2+ catalyst was investigated in order to improve our understanding on the novel metal-independent approach. The interesting and efficient metal-independent hydroxyl radicals (OH) production by using halogenated quinones and H2O2 has been currently demonstrated. The results clearly confirmed the formation of OH radicals from the reaction of CAA with H2O2. CAA was slowly decayed by chemical oxidation with H2O2 and followed a pseudo-first kinetics. H2O2 doses ≥ 1000 mM were required to achieve complete CAA decay from 1 mM CAA. However, low total organic carbon (TOC) removal was measured with the accumulation of carboxylic acids. The addition of Fe2+ enhanced the kinetics of CAA degradation and reduced the required dose of H2O2. High TOC removal was obtained, almost complete release of chloride ions, without accumulation of carboxylic acids. The decolorization of methylene blue (MB) aqueous solutions was performed using H2O2, H2O2/CAA, H2O2/Fe2+, and H2O2/CAA/Fe2+. H2O2/CAA/Fe2+ was the most effective method in decolorizing MB solutions due to the accelerated Fe2+ regeneration. Coupling Fenton reagent with CAA seems to be promising alternative to physical activation in water and soil treatment.

Catalytic Oxidation of Ponceau 4R in Aqueous Solution using Iron-impregnated Al-pillared Bentonite: Optimization of the Process

The application of the Fenton-like process for the oxidation of an aqueous solution of Ponceau 4R dye, using an aluminum pillared clay impregnated with iron (Fe(wt%)/Al-PILC) as catalyst, was investigated. The Response Surface Methodology (RSM), based on a Central Composite Design (CCD) was used to evaluate and optimize the oxidation process of a Ponceau 4R solution. Three independent variables were studied in the experimental design: the amount of H2O2 expressed in multiples of times of stoichiometry dose, iron concentration incorporated by impregnation onto aluminum pillared clay (Fe(wt%)), and amount of catalyst (Fe(wt%)/Al-PILC). The response variables were decolorization and total organic carbon (TOC) removal. The significance of independent variables and their interactions were tested by means of analysis of variance (ANOVA), with a 95% confidence level. With low stoichiometric dose of H2O2 (0.96 and 1.54 times), medium amount of catalyst (374.4 and 391.3 mg) and high Fe concentration impregnated in pillared clay (9.3 and 7.7 wt%), the total decolorization and high TOC removal were achieved. Under multi-objective optimization conditions (3.0 times the stoichiometric dose of H2O2, 420 mg Fe(wt%)/Al-PILC and 5.5 wt% Fe impregnated in Al-PILC), it was possible to achieve 86.18% decolorization and 66.81% TOC removal after 5 h of reaction at 25 °C, with the additional advantage of showing an iron leaching of less than 0.10 mg/L. The established models' soundness is confirmed by a good fit between predictive models and experimental results. Copyright © 2021 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Heteroatom (N, S) Co-Doped CNTs in the Phenol Oxidation by Catalytic Wet Air Oxidation

The N, S-co-doping of commercial carbon nanotubes (CNTs) was performed by a solvent-free mechanothermal approach using thiourea. CNTs were mixed with the N, S-dual precursor in a ball-milling apparatus, and further thermally treated under inert atmosphere between 600 and 1000 °C. The influence of the temperature applied during the thermal procedure was investigated. Textural properties of the materials were not significantly affected either by the mechanical step or by the heating phase. Concerning surface chemistry, the developed methodology allowed the incorporation of N (up to 1.43%) and S (up to 1.3%), distributed by pyridinic (N6), pyrrolic (N5), and quaternary N (NQ) groups, and C–S–, C–S–O, and sulphate functionalities. Catalytic activities of the N, S-doped CNTs were evaluated for the catalytic wet air oxidation (CWAO) of phenol in a batch mode. Although the samples revealed a similar catalytic activity for phenol degradation, a higher total organic carbon removal (60%) was observed using the sample thermally treated at 900 °C. The improved catalytic activity of this sample was attributed to the presence of N6, NQ, and thiophenic groups. This sample was further tested in the oxidation of phenol under a continuous mode, at around 30% of conversion being achieved in the steady-state.

Effect of Operating Parameters, Reaction Kinetics and Comparative Assessment of Fluidized-Bed Fenton Oxidation of 4-Nitrophenol

The oxidation of 4-Nitrophenol (4-NP) has been studied using recirculating fluidized-bed Fenton process. The effect of various parameters such as pH, the concentration of hydrogen peroxide, the concentration of ferrous ions, various types of carriers, and dosage of the carrier were investigated on the oxidation of 4-NP. Al2O3 and SiO2 were used as two different carriers for the oxidation of 4-NP. The experimental results are reported in terms of degradation percentage of 4-NP, Chemical Oxygen Demand (COD), and Total Organic Carbon (TOC). The results showed that the degradation and COD removal of 4-NP in the presence of Al2O3 carrier was higher as compared to SiO2 carrier. The degradation of 96% was achieved under the optimal operating conditions of pH 3, 0.2 mM Fe2+, 4 mM H2O2, and 5g/L of Al2O3 as a carrier. The TOC and COD removals were 70% and 55%, respectively after 1 h of reaction time. The presence of Fe-O bond onto Al2O3 carrier after the reaction was confirmed by the FT-IR studies. The total iron remained in the solution after reaction using fluidized-bed Fenton process was lower (8.5%) than homogeneous Fenton process (17%). The fluidized bed Fenton process also showed higher TOC and COD removal as compared to the homogeneous Fenton process.

Methane recovery from acidic tofu wastewater using an anaerobic fixed-bed reactor with bamboo as the biofilm carrier

Wastewater generated during acid coagulation in tofu processing has high organic concentrations and low pH. Several small industries in Indonesia discharge such wastewater without treatment, necessitating economical treatment to control water pollution. In this study, the feasibility of methane production from the treatment of acidic tofu processing wastewater was investigated. For this, anaerobic treatment of tofu processing wastewater using a fixed-bed reactor employing cut bamboo as the carrier was examined and compared to an upflow anaerobic sludge blanket reactor. Without neutralization, the fixed-bed reactor outperformed the upflow anaerobic sludge blanket reactor at a chemical oxygen demand load of 4.3 kg chemical oxygen demand/m3 day. The highest total organic carbon removal efficiency and methane gas yield were 95% and 0.98 L/g total organic carbon removed, respectively. The two most abundant bacteria were the genus Paludibacter and the unclassified Bacteriodetes; both from the family Porphyromonadaceae. Hydrogenotrophic methanogens from the genera Methanoculleus and Methanobacterium were the dominant archaea, indicating that hydrogenotrophic methanogenesis was a major methane formation pathway.