Search Results (49)

As human living standards have improved, the demand for industrial products—such as food, dyes, cosmetics, pharmaceuticals, and others—has significantly increased. This surge in production has, in turn, led to a rise in industrial wastewater (IW) generation, which is often marked by low biodegradability and a high concentration of toxic or refractory compounds. This review highlights the use of coagulation–flocculation–decantation (CFD) and advanced oxidation processes (AOPs) for treating such wastewater. A comprehensive analysis of CFD is provided, covering the underlying mechanisms, types of coagulants (including metal-based, animal-derived, mineral, and plant-based), and the optimal operational conditions required to maximize treatment efficiency. This review discusses the properties and performance of these coagulants in detail. In addition, this paper explores the methods used in AOPs to reduce organic carbon, focusing particularly on the roles of hydroxyl and sulfate radicals. Emphasis is placed on the enhancement of these processes using radiation, chelating agents, and heterogeneous catalysts, along with their effectiveness in IW treatment. Finally, the integration of CFD as a pre-treatment step to improve the efficiency of subsequent AOPs is provided. Full article

The increasing presence of emerging contaminants in aquatic environments, particularly endocrine disruptors (EDs), has raised significant environmental and public health concerns due to their toxicity, persistence, and ability to interfere with the endocrine systems of both aquatic organisms and humans. Among these compounds, the steroid hormones 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) stand out, as they are frequently detected in wastewater, even after conventional treatment processes, which often exhibit limited removal efficiency. In this context, advanced oxidation processes (AOPs), especially those based on the generation of sulfate radicals (SO₄•⁻), have emerged as promising alternatives due to their high redox potential, extended half-life, and broad effectiveness across various pH levels. This work reviews recent advances in AOPs for the degradation of E2 and EE2, focusing on sulfate radical-based processes. The main degradation mechanisms, operational parameters, removal efficiency, challenges for large-scale application, and gaps in the current literature are discussed. The analysis indicates that despite their high effectiveness, sulfate radical-based processes still require further investigation in real wastewater matrices, the assessment of the toxicity of by-products, and the optimization of operational variables to be established as viable and sustainable technologies for wastewater treatment. Full article

A novel amorphous Fe-doped manganese carbonate (a-FeMn-1) was synthesized via a facile co-precipitation method and evaluated as an efficient heterogeneous catalyst for the activation of peroxymonosulfate (PMS) in the degradation of Orange II. Among various Fe/Mn molar ratios, the 1:1 composition (a-FeMn-1) showed optimal catalytic activity, achieving 98% removal efficiency within 60 min under near-neutral pH conditions. Characterization results indicated that Fe doping effectively induced an amorphous structure and increased surface area and oxygen defects, promoting PMS activation. The system displayed broad pH applicability and resistance to Cl⁻ and natural organic matter, while degradation was inhibited by HCO₃⁻ and PO₄³⁻. EPR and quenching experiments confirmed that surface-bound sulfate radicals (SO₄^•−), hydroxyl radicals (^•OH), and singlet oxygen (¹O₂) were the primary reactive species. XPS analysis further revealed the redox cycling of Fe and Mn and the involvement of defect oxygen in the PMS activation process. The catalyst also demonstrated excellent reusability over five cycles without significant loss in efficiency. This work provides insights into the rational design of amorphous bimetallic materials for sulfate radical-based advanced oxidation processes. Full article

Extensive utilization of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) has resulted in contamination of the aquatic environment; this situation requires effective treatment technology. Ultraviolet-based advanced oxidation processes (UV-AOPs) are widely employed for the removal of organic contaminants from water. This study’s aim was to compare the degradation of the pesticide 2,4-D in UV-C-activated peroxide and peroxydisulfate systems. UV-C irradiation alone exhibited a negligible effect on pesticide degradation, whereas the addition of oxidants significantly enhanced the degradation efficiency relative to 2,4-D. Complete pesticide removal was achieved after 15 min of UV/H₂O₂ treatment, while twice as much time was required with the UV/S₂O₈²⁻ process. COD decreased by 74% and 28% for UV-C-activated peroxide and peroxydisulfate, respectively. Both investigated systems demonstrated good performance for 2,4-D dechlorination. Pesticide degradation rates increased with increasing dosages of the applied oxidants. Acidic conditions were more favorable for degradation of 2,4-D, compared to neutral and basic conditions, for both systems studied. The degradation efficiency relative to 2,4-D decreased in the presence of HA, Cl⁻ and HCO₃⁻ in water matrices. The predominant radical for the UV-C-activated peroxydisulfate was determined to be a sulfate radical. These findings are of fundamental and practical significance in understanding UV-C-activated 2,4-D degradation, paving the way for the selection of preferred processes for the optimal removal of pesticides from various aqueous matrices. Full article

Global industrialization has intensified the emission of emerging contaminants (ECs), posing a serious threat to the environment and human health. Persulfate-based advanced oxidation processes (PS-AOPs) have become a research hotspot due to their efficient degradation capability and environmentally friendly features; carbon-based materials are ideal catalysts for activating persulfate (PS) due to their tunable electronic structure, abundant active sites, and low cost. This study summarizes the application of carbon-based materials (graphene, single-atom catalysts (SACs), etc.) in PS-AOPs, and provides insights into the degradation mechanisms of radicals (e.g., sulfate radical (SO₄^−·), hydroxyl radical (·OH)) and non-radicals (e.g., ¹O₂(singlet oxygen), electron transfer). The removal efficacy of carbon-based catalysts for antibiotics, phenols, and dyes was compared, and the key degradation pathways were elucidated. In addition, the activation of PS can be accelerated, and catalytic efficiency can be improved by synergizing with ancillary technologies (e.g., light, electricity). Despite the great potential of carbon-based catalysts, their large-scale application is limited by the complexity of the catalyst preparation process and the lack of selectivity for complex water qualities. Future studies can accelerate the practical application of PS-AOPs in wastewater treatment through the precise design of SACs and the construction of multi-mechanism synergistic activation systems. Full article

This study optimized the proportions of synergistic catalysts to efficiently activate potassium peroxymonosulfate (Oxone), generate more reactive oxygen species, and accelerate the chemical oxidation of silicon carbide (4H-SiC) wafers during chemical–mechanical polishing (CMP) for an improved material removal rate (MRR) and surface quality. The Oxone was activated using ultraviolet (UV) catalysis with a photocatalyst (TiO₂) and transition metal (Fe₃O₄) to enhance the oxidation capacity of the polishing slurry through the production of strong oxidizing sulfate radicals (${\mathrm{S}\mathrm{O}}_4^{·-}$). First, the effects of the TiO₂, Fe₃O₄, and Oxone concentrations on the MRR were studied by conducting multiple single-factor experiments. Next, 4H-SiC wafers were polished using different catalyst combinations to verify the synergistic activation of Oxone by multiple catalysts. Finally, the roughnesses, physical features, and elemental compositions of the wafer surfaces were observed before and after polishing. The results showed that CMP with a TiO₂ concentration of 0.15 wt%, Fe₃O₄ concentration of 0.75 wt%, and Oxone concentration of 48 mM decreased the wafer surface roughness from Sa 134 to 8.251 nm and achieved a maximum MRR of 2360 nm/h, which is significantly higher than that associated with traditional CMP methods. The surface of a 4H-SiC wafer polished using CMP with the optimal catalytic system was extremely smooth with no scratches and exhibited many oxides that reduced its hardness. In summary, the proposed UV-TiO₂-Fe₃O₄-Oxone composite catalytic system for 4H-SiC CMP exhibited significant synergistic enhancements and demonstrated excellent surface quality, indicating considerable potential for the polishing of hard materials. Full article

Advanced oxidation processes (AOPs) based on activated persulfate (PS) are gradually being employed in the treatment of novel pollutants. In this study, an efficient and reliable CoNiFe-layered double hydroxide (LDH) was prepared by a hydrothermal method, which could effectively activate peroxomonosulfate (PMS) and cause free sulfate radical (SO₄^•−) oxidation to decompose atrazine (ATZ). The degradation rate of ATZ was greater than 99% within 60 min at pH 7 when the initial concentration of ATZ was 10 mg·L⁻¹, and the dosages of PMS and activator were 0.6 mM and 80 mg·L⁻¹. The analysis of ATZ degradation confirmed the reusability of the activator and its strong structural stability. The generation of four free radicals was analyzed and confirmed, and the influence on the degradation reaction was SO₄^•− > O₂^•− > ¹O₂ > •OH. The analytical results showed that the metal ions reacted with HSO₅⁻ in PMS to cause an oxidation–reduction cycle change in the valence state of the metal ions and generated the primary factor affecting the degradation reaction—SO₄^•−. Nine degradation intermediates with reduced toxicity were detected and possible ATZ degradation pathways were deduced, thus confirming the activation mechanism of CoNiFe-LDH. Full article

As the most promising techniques for refractory antibiotic degradation in wastewater management, sulfate radical-based advanced oxidation processes (SR-AOPs) have attracted considerable attention. However, systematic studies on potassium peroxymonosulfate (PMS) activation by MOF-derived metal oxides coated with LDH materials are still lacking. In this work, a series of catalysts consisting of CoCu-MOFs coated with CuAl/LDH were synthesized for PMS activation in the removal of sulfamethoxazole (SMX). As expected, CoCu-MOFs coated with CuAl/LDH catalyst showed high SMX removal and stability in PMS activation. In the CoCu/LDH/PMS reaction, the SMX removal was nearly 100% after 60 min, and the mineralization reached 53.7%. The catalyst showed excellent catalytic stability and low metal leaching concentrations (Co: 0.013 mg/L, Cu: 0.313 mg/L), as detected by ICP. Sulfate radicals and hydroxyl radicals were identified as the dominant reactive species in the CoCu/LDH/PMS system. Moreover, the presence of ¹O₂ in the process revealed the coupling of non-radical and radical processes. The XPS results showed that the layered structure of CoCu/LDH promoted the recycling of metal ions (high and low valence), which facilitated heterogeneous PMS activation. The effects of different reaction conditions and reuse cycles were also determined. The SMX oxidation pathways were proposed based on the intermediates identified by LC/MS. The high activity and stability of CoCu/LDH provide a new mechanistic understanding of PMS activation catalysts and their potential utilization in practical wastewater treatment. Full article

Persulfate-based advanced oxidation processes have emerged as a promising approach for the degradation of organic pollutants in aqueous environments due to their ability to generate sulfate radicals (SO₄^−·) within catalytic systems. In this study, peroxydisulfate (PDS) and peroxymonosulfate (PMS) were investigated with the natural vanadium–titanium magnetite (VTM) as the activator for the degradation of acid orange II. The degradation efficiency increased with higher dosages of VTM or persulfate (both PDS and PMS) at lower concentrations (below 10 mM). However, excessive PMS (higher than 10 mM) in the PMS/VTM system led to the self-consumption of free radicals, significantly inhibiting the degradation of acid orange II. The VTM-activated PDS or PMS maintained an effective degradation of acid orange II in a wide pH range (3~11), suggesting remarkable pH stability. The SO₄^−· was the main active species in the PDS/VTM system, while hydroxyl radical (·OH) also contributed significantly to the PMS/VTM system. In addition, PMS exhibited better thermal stability during VTM activation. Coexisting ions in an aqueous environment such as bicarbonate (HCO₃^–), carbonate (CO₃^2–), and hydrogen phosphate (HPO₄^2–) had obvious effects on persulfate activation. Our study systematically investigated the different activation processes and influencing factors associated with PDS and PMS when the natural VTM was used as a catalyst, thereby providing new insights into the persulfate-mediated degradation of organic pollutants in aqueous environments. Full article

The widespread environmental contamination resulting from the misuse of tetracycline antibiotics (TCs) has garnered significant attention and study by scholars. Photocatalytic technology is one of the environmentally friendly advanced oxidation processes (AOPs) that can effectively solve the problem of residue of TCs in the water environment. This study involved the synthesis of the heterogeneous magnetic photocatalytic material of CoFe₂O₄/NaBiO₃ via the solvothermal method, and it was characterized using different characterization techniques. Then, the photocatalytic system under visible light (Vis) was coupled with peroxymonosulfate (PMS) to explore the performance and mechanism of degradation of tetracycline hydrochloride (TCH) in the wastewater. The characterization results revealed that CoFe₂O₄/NaBiO₃ effectively alleviated the agglomeration phenomenon of CoFe₂O₄ particles, increased the specific surface area, effectively narrowed the band gap, expanded the visible light absorption spectrum, and inhibited recombination of photogenerated electron–hole pairs. In the Vis+CoFe₂O₄/NaBiO₃+PMS system, CoFe₂O₄/NaBiO₃ effectively activated PMS to produce hydroxyl radicals (·OH) and sulfate radicals (SO₄⁻). Under the conditions of a TCH concentration of 10 mg/L⁻¹, a catalyst concentration of 1 g/L⁻¹ and a PMS concentration of 100 mg/L⁻¹, the degradation efficiency of TCH reached 94% after 100 min illumination. The degradation of TCH was enhanced with the increase in the CoFe₂O₄/NaBiO₃ and PMS dosage. The solution pH and organic matter had a significant impact on TCH degradation. Notably, the TCH degradation efficiency decreased inversely with increasing values of these parameters. The quenching experiments indicated that the free radicals contributing to the Vis+CoFe₂O₄/NaBiO₃+PMS system were ·OH followed by SO₄⁻, hole (h⁺), and the superoxide radical (O₂⁻). The main mechanism of PMS was based on the cycle of Co³⁺ and Co²⁺, as well as Fe³⁺ and Fe²⁺. The cyclic tests and characterization by XRD and FT-IR revealed that CoFe₂O₄/NaBiO₃ had good degradation stability. The experimental findings can serve as a reference for the complete removal of antibiotics from wastewater. Full article

Sulfate radical-based advanced oxidation processes exhibit great potential for the degradation of organic pollutants. In this study, P-doped biochar (PBC500) was successfully synthesized by the pyrolysis of H₃PO₄-impregnated cow manure waste and was employed to activate peroxymonosulfate (PMS) for the elimination of 17β-estradiol (E2). The characterization results showed that the surface area, defective structure, and functional groups (C=O and phosphorus-containing groups) of biochar increased after H₃PO₄ modification. PBC500 exhibited high PMS activation activity and excellent E2 degradation capacity; 97.91% of 3 mg/L E2 can be removed within 90 min using 0.2 g/L PBC500 and 1 mM PMS. Based on the quenching experiments and X-ray photoelectron spectroscopy (XPS) analysis, defective structures, C=O, and P-C groups on biochar act as active sites to promote the catalytic oxidation of E2 by generating O₂⁻ and ¹O₂. In addition, PBC500 displayed excellent reusability, achieving 65.15% E2 degradation after three reuse cycles. Overall, this study presented a new technique that supports a high efficiency, environmentally friendly, and low cost treatment method for E2 wastewater and simultaneously provided a new option for the resource utilization of livestock waste. Full article

Persulfate-based advanced oxidation process has been proven to be a promising method for the toxic pesticide chlorpyrifos (CPY) degradation in wastewater treatment. However, due to the limitation for the short-lived intermediates detection, a comprehensive understanding for the degradation pathway remains unclear. To address this issue, density functional theory was used to analyze the degradation mechanism of CPY at the M06-2X/6-311++G(3df,3pd)//M06-2X/6-31+G(d,p) level, and computational toxicology methods were employed to explore the toxicity of CPY and its degradation products. Results show that hydroxyl radicals (·OH) and sulfate radicals (SO₄^•−) initiate the degradation reactions by adding to the P=S bond and abstracting the H atom on the ethyl group, rather than undergoing α-elimination of the pyridine ring in the persulfate oxidation process. Moreover, the addition products were attracted and degraded by breaking the P–O bond, while the abstraction products were degraded through dealkylation reactions. The transformation products, including 3,5,6-trichloro-2-pyridynol, O,O-diethyl phosphorothioate, chlorpyrifos oxon, and acetaldehyde, obtained through theoretical calculations have been detected in previous experimental studies. The reaction rate constants of CPY with ·OH and SO₄^•− were 6.32 × 10⁸ and 9.14 × 10⁸ M⁻¹·s⁻¹ at room temperature, respectively, which was consistent with the experimental values of 4.42 × 10⁹ and 4.5 × 10⁹ M⁻¹ s⁻¹. Toxicity evaluation results indicated that the acute and chronic toxicity to aquatic organisms gradually decreased during the degradation process. However, some products still possess toxic or highly toxic levels, which may pose risks to human health. These research findings contribute to understanding the transformation behavior and risk assessment of CPY in practical wastewater treatment. Full article

Nowadays, antibiotics are widely used, increasing the risk of contamination of the water body and further threatening human health. The traditional water treatment process is less efficient in degrading antibiotics, and the advanced oxidation process (AOPs) is cleaner and more efficient than the traditional biochemical degradation process. The combined ozone/peroxymonosulfate (PMS) advanced oxidation process (O₃/PMS) based on sulfate radical (SO₄^•−) and hydroxyl radical (•OH) has developed rapidly in recent years. The O₃/PMS process has become one of the most effective ways to treat antibiotic wastewater. The reaction mechanism of O₃/PMS was reviewed in this paper, and the research and application progress of the O₃/PMS process in the degradation of antibiotics in drinking water and wastewater effluent were evaluated. The operation characteristics and current application range of the process were summarized, which has a certain reference value for further research on O₃/PMS process. Full article

Remediation of organic dyes in natural waters is a significant environmental need under active study. This review analyzes bimetallic catalytic degradation systems that are based on the Fenton chemistry concept and that generate reactive oxygen species (ROS) as the agent of dye breakdown. Recently developed advanced oxidation processes (AOPs) take advantage of bimetallic heterogeneous catalysts to facilitate rapid rates and full degradation. Catalysts based on two metals including iron, copper, molybdenum, cobalt and magnesium are discussed mechanistically as examples of effective radical ROS producers. The reactive oxygen species hydroxyl radical, superoxide radical, sulfate radical and singlet oxygen are discussed. System conditions for the best degradation are compared, with implementation techniques mentioned. The outlook for further studies of dye degradation is presented. Full article

In recent years, due to the high consumption of drugs both for human needs and for their growing use, especially as regards antibiotics, in the diet of livestock, water pollution has reached very high levels and attracted widespread attention. Drugs have a stable chemical structure and are recalcitrant to many treatments, especially biological ones. Among the methods that have shown high efficiency are advanced oxidation processes (AOPs) which are, among other things, inexpensive and eco-friendly. AOPs are based on the production of reactive oxygen species (ROS) able to degrade organic pollutants in wastewater. The main problem related to the degradation of drugs is their partial oxidation to compounds that are often more harmful than their precursors. In this review, which is not intended to be exhaustive, we provide an overview of recent advances in the removal of organic drugs via advanced oxidation processes (AOPs). The salient points of each process, highlighting advantages and disadvantages, have been summarized. In particular, the use of AOPs such as UV, ozone, Fenton-based AOPs and heterogeneous photocatalysis in the removal of some of the most common drugs (tetracycline, ibuprofen, oxytetracycline, lincomycin) has been reported. Full article