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In situ vaccine (ISV) can provoke systemic anti-tumor immunity through the induction of immunogenic cell death (ICD). The development of ISV technology has been restricted by the limited and suboptimal ICD driven tumor antigen production which are currently relying on chemo-drugs, photo-/radio-sensitizers, oncolytic-virus and immunostimulatory agents. Herein, a sulfate radical (SO4 ·-) based ISV is reported that accomplishes superior tumor immunotherapy dispense from conventional approaches. The ISV denoted as P-Mn-LDH is constructed by intercalating peroxydisulfate (PDS, a precursor of SO4 ·-) into manganese layered double hydroxide nanoparticles (Mn-LDH). This design allows the stabilization of PDS under ambient condition, but triggers a Mn2+ mediated PDS decomposition in acidic tumor microenvironment (TME) to generate in situ SO4 ·-. Importantly, it is found that the SO4 ·- radicals not only effectively kill cancer cells, but also induce a necroptotic cell death pathway, leading to robust ICD signaling for eliciting adaptive immunity. Further, the P-Mn-LDH can activate the stimulator of interferon genes (STING) pathway to further boost anti-tumor immunity. Collectively, the P-Mn-LDH based ISV exhibited potent activity in inhibiting tumor growth and lung metastasis. When combined with immune checkpoint inhibitor, significant inhibition of distant tumors is achieved. This study underpins the promise of SO4 ·- based vaccine technology for cancer immunotherapy.

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Biochar coupled with peroxymonosulfate (PMS) to produce sulfate radicals and its application to urban wastewater disinfection has been rarely investigated and no information is available about microplastics (MPs) interference on the disinfection process. In this study, FeCl3-activated biochar (Fe-BC) was coupled to PMS to evaluate the inactivation of Escherichia coli (E. coli) in real secondary treated urban wastewater. Surface morphology of Fe-BC sample, characterized by Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS), showed a rough texture with uniform distribution of iron particles over the entire surface area. E. coli inactivation improved (∼3.8 log units, detection limit = 1 CFU/100 mL) as Fe-BC concentration was decreased (from 1.0 g/L to 0.5 g/L), at a constant PMS dose (300 mg/L). Besides, removal efficiency of E. coli was negatively affected by the presence of small (30-50 µm) polyethylene MPs (PE MPs) (200 mg/L), which could be attributed to the adsorption of MPs on Fe-BC surface, according to SEM images of post-treated Fe-BC. The low disinfection efficiency of Fe-BC/PMS system in presence MPs could be due to blocking of Fe-BC sites for PMS activation and/or radicals scavenging during treatment. These results allowed to unveil the mechanisms of MPs interference on E. coli inactivation by Fe-BC/PMS, as well as the potential of this process to make the effluent in compliance with the stringent limit for agricultural reuse.

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Developing a high-performance activator is crucial for the practical application of peroxymonosulfate-based advanced oxidation processes (PMS-AOPs). High-entropy oxides (HEOs) have attracted increasing attention due to their stable crystal structure, flexible composition and unique functionality. However, research into the mechanisms by which HEOs function as PMS activators for degrading organic pollutants remains insufficient, and the relationship between entropy and the catalytic performance of HEOs has yet to be clarified. In this study, we synthesized NiMgZnCuCoOx with different levels of entropy as PMS activators for acetaminophen (APAP) degradation, and observed a significant effect for entropy on the catalytic performance. Sulfate radicals (SO4•‒) were identified as the primary reactive oxygen species (ROS), while hydroxyl radicals (•OH) and singlet oxygen (1O2) act as secondary ROS during APAP degradation. Both the Co2+ contents and the oxygen vacancy concentration in NiMgZnCuCoOx are found to increase with the entropy. An increase in the Co2+ sites leads to more activation sites for PMS activation, while excessive oxygen vacancies consume PMS, producing weak oxidation species, and affect the electron-donating ability of Co2+. Consequently, the NiMgZnCuCoOx with middle level of entropy exhibits the optimal performance with APAP degradation rate and mineralization rate reaching 100% and 74.22%, respectively. Furthermore, the degradation intermediates and their toxicities were assessed through liquid chromatography-mass spectrometry and quantitative structure-activity relationship analysis. This work is expected to provide critical insight into the impact of the HEOs entropy on the PMS activation and guide the rational design of highly efficient peroxymonosulfate activators for environmental applications.

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Widespread use of tetracycline (TC) results in its persistent residue and bioaccumulation in aquatic environments, posing a high toxicity to non-target organisms. In this study, a bimetal-doped composite material Ag3PO4/MIL-101(Fe,Cu) has been designed for the treatment of TC in aqueous solutions. As the molar ratio of Fe/Cu in composite is 1:1, the obtained material AP/MFe1Cu1 is placed in an aqueous environment under visible light irradiation in the presence of 3 mM peroxydisulfate (PDS), which forms a photo-Fenton-like catalytic system that can completely degrade TC (10 mg/L) within 60 min. Further, the degradation rate constant (0.0668 min-1) is 5.66 and 7.34 times higher than that of AP/MFe and AP/MCu, respectively, demonstrating a significant advantage over single metal-doped catalysts. DFT calculations confirm the strong adsorption capacity and activation advantage of PDS on the composite surface. Therefore, the continuous photogenerated electrons (e-) accelerate the activation of PDS and the production of SO4•-, resulting in the stripping of abundant photogenerated h + for TC oxidation. Meanwhile, the internal circulation of FeⅢ/FeⅡ and CuⅡ/CuⅢ in composite also greatly enhances the photo-Fenton-like catalytic stability. According to the competitive dynamic experiments, SO4•- have the greatest contribution to TC degradation (58.93%), followed by 1O2 (23.80%). The degradation intermediates (products) identified by high-performance liquid chromatography-mass spectrometry (HPLC/MS) technique indicate the involvement of various processes in TC degradation, such as dehydroxylation, deamination, N-demethylation, and ring opening. Furthermore, as the reaction proceeds, the toxicity of the intermediates produced during TC degradation gradually decreases, which can ensure the safety of the aquatic ecosystem. Overall, this work reveals the synergy mechanism of PDS catalysis and photocatalysis, as well as provides technical support for removal of TC-contaminated wastewater.

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If trace amounts of antibiotics remain in the environment, they can lead to microbial pathogens becoming resistant to antibiotics and putting ecosystem health at risk. For instance, ciprofloxacin (CIP) can be found in surface and ground waters, suggesting that conventional water treatment technologies are ineffective at removing it. Now, a rGO/g-C3N4/SiO2 nanocomposite was synthesized in this study to activate peroxydisulfate (PDS) under UVA-LED irradiation. UVA-LED/rGO-g-C3N4-SiO2/PDS system performance was evaluated using Ciprofloxacin as an antibiotic. Particularly, rGO/g-C3N4/SiO2 showed superior catalytic activity for PDS activation to remove CIP. Operational variables, reactive species determination, and mechanisms were investigated. 0.85 mM PDS and 0.3 g/L rGO/g-C3N4/SiO2 eliminated 99.63% of CIP in 35 min and mineralized 59.78% in 100 min at pH = 6.18. By scavenging free radicals, bicarbonate ions inhibit CIP degradation. According to the trapping experiments, superoxide (O2•-) was the main active species rather than sulfate (SO4•-) and hydroxyl radicals (•OH). RGO/g-C3N4/SiO2 showed an excellent recyclable capability of up to six cycles. The UVA-LED/rGO-g-C3N4-SiO2/PDS system was also tested under real conditions. The system efficiency was reasonable. By calculating the synergistic factor (SF), this work highlights the benefit of combining composite, UVA-LED, and PDS. UVA-LED/rGO-g-C3N4-SiO2/PDS had also been predicted to be an eco-friendly process based on the results of the ECOSAR program. Consequently, this study provides a novel and durable nanocomposite with supreme thermal stability that effectively mitigates environmental contamination by eliminating antibiotics from wastewater.

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The sulfate radical (SO4•-), known for its high reactivity and long lifespan, has emerged as a potent antimicrobial agent. Its exceptional energy allows for the disruption of vital structures and metabolic pathways in bacteria that are usually inaccessible to common radicals. Despite its promising potential, the efficient generation of this radical, particularly through methods involving enzymes and photocatalysis, remains a substantial challenge. Here, we capitalized on the peroxidase (POD)-mimicking activity and photocatalytic properties of cerium oxide (CeO2) nanozymes, integrating these properties with the enhanced concept of plasma gold nanorod (GNR) to develop a half-encapsulated core@shell GNRs@CeO2 Janus heterostructure impregnated with persulfate. Under near-infrared irradiation, the GNRs generate hot electrons, thereby boosting the CeO2's enzyme-like activity and initiating a potent reactive oxygen species (ROS) storm. This distinct nanoarchitecture facilitates functional specialization, wherein the heterostructure and efficient light absorption ensured continuous hot electron flow, not only enhancing the POD-like activity of CeO2 for the production of SO4•- effectively, but also contributing a significant photothermal effect, disrupting periodontal plaque biofilm and effectively eradicating pathogens. Furthermore, the local temperature elevation synergistically enhances the POD-like activity of CeO2. Transcriptomics analysis, as well as animal experiments of the periodontitis model, have revealed that pathogens undergo genetic information destruction, metabolic disorders, and pathogenicity changes in the powerful ROS system, and profound therapeutic outcomes in vivo, including anti-inflammation and bone preservation. This study demonstrated that energy transfer to augment nanozyme activity, specifically targeting ROS generation, constitutes a significant advancement in antibacterial treatment.

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In persulfate-based advanced oxidation processes (PS-AOPs), sulfate radicals (SO4•-) have been recognized to play more important roles in inducing bromate (BrO3-) formation rather than hydroxyl radicals (HO•) because of the stronger oxidation capacity of the former. However, this study reported an opposite result that HO• indeed dominated the formation of bromate instead of SO4•-. Quenching experiments were coupled with electron paramagnetic resonance (EPR) detection and chemical probe identification to elucidate the contributions of each radical species. The comparison of different thermal activated persulfates (PDS and PMS) demonstrated that the significant higher bromate formation in HEAT/PMS ([BrO3-]/[Br-]0 = 0.8), as compared to HEAT/PDS ([BrO3-]/[Br-]0 = 0.2), was attributable to the higher concentration of HO• radicals in HEAT/PMS. Similarly, the bromate formation in UV/PDS ([BrO3-]/[Br-]0 = 1.0), with a high concentration of HO•, further underscored the dominant role of HO•. As a result, we quantified that HO• and SO4•- radicals accounted 66.7% and 33.3% for bromate formation. This controversial result can be reconciled by considering the critical intermediate, hypobromic acid/hypobromate (HOBr/BrO-), involved in the transformation of Br- to BrO3-. HO• radicals have the chemical preference to induce the formation of HOBr/BrO- intermediates (contributing âˆ¼ 60%) relative to SO4•- radicals (contributing âˆ¼ 40%). This study highlighted the dominant role of HO• in the formation of bromate rather than SO4•- in PS-AOPs and potentially offered novel insights for reducing disinfection byproduct formation by controlling the radical species in AOPs.

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Natural organic matter (NOM) is a major sink of radicals in advanced oxidation processes (AOPs) and understanding the transformation of NOM is important in water treatment. By using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) in conjunction with machine learning, we comprehensively investigated the reactivity and transformation of NOM, and the formation of organosulfates during the UV/peroxydisulfate (PDS) process. After 60 min UV/PDS treatment, the CHO formula number and dissolved organic carbon concentration significantly decreased by 83.4 % and 74.8 %, respectively. Concurrently, the CHOS formula number increased substantially from 0.7 % to 20.5 %. Machine learning identifies DBE and AImod as the critical characteristics determining the reactivity of NOM during UV/PDS treatment. Furthermore, linkage analysis suggests that decarboxylation and dealkylation reactions are dominant transformation pathways, while the additions of SO3 and SO4 are also non-negligible. According to SHAP analysis, the m/z, number of oxygens, DBE and O/C of NOM were positively correlated with the formation of organosulfates in UV/PDS process. 92 organosulfates were screened out by precursor ion scan of HPLC-MS/MS and verified by UPLC-Q-TOF-MS, among which, 7 organosufates were quantified by authentic standards with the highest concentrations ranging from 2.1 to 203.0 ng L‒1. In addition, the cytotoxicity of NOM to Chinese Hamster Ovary (CHO) cells increased by 13.8 % after 30 min UV/PDS treatment, likely responsible for the formation of organosulfates. This is the first study to employ FT-ICR MS combined with machine learning to identify the dominant NOM properties affecting its reactivity and confirmed the formation of organosulfates from sulfate radical oxidation of NOM.

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The rampant upsurge of organic pollutants in aqueous media has become one of the major concerns nowadays. Finding non-specific catalysts that can target a wide range of organic pollutants is a key challenge. Eco-friendly oxidative radicals, such as promoted by peroxymonosulfate (PMS), are necessary for efficient water decontamination. We propose a multicomponent composite catalyst for activating PMS using a dual strategy of sonophotocatalysis. The composite integrates cobalt ferrite and Cu- or Ce-doped SnO2, with the at. % of doping metal and the mixture ratio carefully balanced. The top-performing architectures were able to decompose rhodamine B (20 ppm), a representative pollutant, in under 3 min and achieve over 70% mineralization in just 5 min. The synthesized nanocomposites demonstrated exceptional sonophotocatalytic performance, even when treating complex and diverse multipollutant solutions (80 ppm), achieving over 75% mineralization after 150 min. Considering their high stability and reusability, the proposed CoFe2O4/Cu- and Ce-doped SnO2 materials are among the state-of-the-art heterogeneous catalysts for mineralizing organic pollutants through PMS activation.

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The catalyst's composition and rationally designed structure is significantly interlinked with its performance for wastewater remediation. Here, a novel hollow cobalt phosphides/carbon (HCoP/C) as an efficient catalyst for activating peroxymonosulfate (PMS) was prepared. The ZIF-67 was synthesized first, followed by phytic acid (PA) etching and then heat treatment was used to get HCoP/C. The PA was used as an etching agent and a source of phosphorus to prepare HCoP/C. To analyze catalytic performance, another solid cobalt phosphides/carbon (SCoP/C) catalyst was prepared for comparison. In contrast to SCoP/C, the HCoP/C exhibited higher catalytic efficiency when used to activate PMS to degrade Bisphenol A (BPA). The results showed that about 98 % of targeted pollutant BPA was removed from the system in 6 min with a rate constant of 0.78 min-1, which was 4 times higher than the solid structure catalyst. The higher catalytic performance of HCoP/C is attributed to its hollow structure. In the study, other parameters such as BPA concentration, temperature, pH, and different catalyst amount were also tested. Moreover, the electron paramagnetic resonance (EPR) and radical quenching analysis confirmed that sulfate radicals were dominant in the HCoP/C/PMS system.

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Waste activated sludge properties vary widely with different regions due to the difference in living standards and geographical distribution, making a big challenge to developing a universally effective sludge dewatering technique. The Fe(II)-activated persulfate (S2O82-) oxidation process shows excellent ability to disrupt sludge cells and extracellular polymeric substances (EPS), and release bound water from sludge flocs. In this study, the discrepancies in the physicochemical characteristics of sludge samples from seven representative cities in China (e.g., dewaterability, EPS composition, surface charge, microbial community, relative abundance of antibiotic resistance genes (ARGs), etc.) were investigated, and the role of Fe(II)-S2O82- oxidation in enhancing removal of antibiotic resistance genes and dewatering ability were explored. The results showed significant differences between the EPS distribution and chemical composition of sludge samples due to different treatment processes, effluent sources, and regions. The Fe(II)-S2O82- oxidation pretreatment had a good enhancement of sludge dewatering capacity (up to 76 %). Microbial analysis showed that the microbial community in each sludge varied significantly depending on the types of wastewater, the wastewater treatment processes, and the regions, but Fe(II)-S2O82- oxidation was able to attack and rupture the sludge zoogloea indiscriminately. Genetic analysis further showed that a considerable number of ARGs were detected in all of these sludge samples and that Fe(II)-S2O82- oxidation was effective in removing ARGs by higher than 90 %. The highly active radicals (e.g., SO4-·, ·OH) produced in this process caused drastic damage to sludge microbial cells and DNA stability while liberating the EPS/cell-bound water. Co-occurrence network analysis highlighted a positive correlation between population distribution and ARGs abundance, while variations in microbial communities were linked to regional differences in living standards and level of economic development. Despite these variations, the Fe(II)-S2O82- oxidation consistently achieved excellent performance in both ARGs removal and sludge dewatering. The significant modularity of associations between different microbial communities also confirms its ability to reduce horizontal gene transfer (HGT) by scavenging microbes.

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Textile wastewater, heavily contaminated with organic dyes, is generating severe problems to environment and human health. The implementation of gC3N4 with biochar (gC3N4-BC) for the treatment of textile wastewater is less effective due to the limited adsorption capacity and slower degradation kinetics. To tackle these problems, peroxydisulfate (PDS) is integrated with gC3N4-BC photocatalyst to enhance the process efficiency and kinetics. The synthesized gC3N4-BC-5 composite shows higher separation of charge carriers, light absorbance, and lower energy bandgap (2.62 eV). The results of photocatalytic degradation and rate constant are enhanced up to 99.9 % and 0.041 min-1 using gC3N4-BC-5 with PDS as compared to without PDS (96.8 % and 0.028 min-1, respectively). The radicals (SO4-•,O2-•, and OH•) are responsible to improve the degradation process efficiency and kinetics. The reusability of optimized sample indicates that gC3N4-BC-5 is stable and effective up to five cycles. The gC3N4-BC-5 composite attains highest adsorption (70.9 %) when compared to BC (62.3 %) and pure gC3N4 (27.1 %). The well-fitted models of adsorption (Pseudo-Second-Order and Freundlich) confirm the favorable, chemical, and multilayered adsorption process. The coupling of gC3N4-BC-5 with PDS is effective, efficient, and stable process to enhance the kinetics and degradation of textile wastewater.

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This study focuses on the treatment of secondary urban wastewater (W) to improve the effluent quality aiming at the reduction of pathogenic microorganisms for the safe reuse of the treated wastewater (TW). Catalyst-free persulfate activation by radiation-based oxidation was applied as a treatment technology. A parametric study was carried out to select the best operating conditions. Total enterobacteria inactivation (quantified by the log reduction (CFU/100 mL)) was achieved when using [S2O82-] = 1 mM, pH = 8.5 (natural pH of W), T = 25 °C, and I = 500 W/m2. However, storing TW for 3 days promoted the regrowth of bacteria, risking its reutilization. Therefore, in this study, and for the first time, the potential beneficial role of inoculation of wastewater treated by the radiation-activated persulfate process with a diverse bacterial community was evaluated in order to control the regrowth of potentially harmful microorganisms through bacterial competition. For this, TW was diluted with river water (R) in the volume percentages of 5, 25, and 50 (percentages refer to R content), and enterobacteria and total heterotrophs were enumerated before and after storage for 72 h. The results showed total heterotrophs and enterobacteria regrowth for TW and R + TW diluted 5 and 25% after storage. However, for R + TW diluted 50%, only the total heterotrophs regrew. Hence, the treated wastewater generated by the oxidative process diluted with 50% river water complies with the legislated limits for reuse in urban uses or irrigation.

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We report a protocol for alkene hydroxyalkenylation. Using a persulfate anion as a one-electron-oxidation reagent and 1,2-bis(phenylsulfonyl)ethylene as a radical acceptor in the presence of water, alkenes were converted into the corresponding 1-phenylsulfonyl-4-hydroxyalkenes in good to high yields. The hydroxyalkenylation process involves the nucleophilic hydroxylation of alkene radical cations to give ß-hydroxyalkyl radicals, which, after a radical addition/ß-elimination sequence, provide the products. We also report a photocatalytic protocol for alkoxyalkenylation.

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As a class of organic micropollutants of global concern, pharmaceuticals have prevalent distributions in the aqueous environment (e.g., groundwater and surface water) and solid matrices (e.g., soil, sediments, and dried sludge). Their contamination levels have been further aggravated by the annually increased production of expired drugs as emerging harmful wastes worldwide. Sulfate radicals (SO4•-)-based oxidation has attracted increasing attention for abating pharmaceuticals in the environment, whereas the transformation mechanisms of solid-phase pharmaceuticals remain unknown thus far. This investigation presented for the first time that SO4•-, individually produced by mechanical force-activated and heat-activated persulfate treatments, could effectively oxidize three model pharmaceuticals (i.e., methotrexate, sitagliptin, and salbutamol) in both solid and liquid phases. The high-resolution mass spectrometric analysis suggested their distinct transformation products formed by different phases of SO4•- oxidation. Accordingly, the SO4•--mediated mechanistic differences between the solid-phase and liquid-phase pharmaceuticals were proposed. It is noteworthy that the products from both systems were predicted with the remaining persistence, bioaccumulation, and multi-endpoint toxicity. Therefore, some post-treatment strategies need to be considered during practical applications of SO4•--based technologies in remediating different phases of micropollutants. This work has environmental implications for understanding the comparative transformation mechanisms of pharmaceuticals by SO4•- oxidation in remediating the contaminated solid and aqueous matrices.

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The development of heterogeneous Co-based catalysts with an effective combination mode of Co/Fe and supporter, a facile synthetic method, and a low treatment cost is an important environment challenge for azo dyes degradation by peroxymonosulfate (PMS) activation. In this study, NaA zeolite supported CoxFey with various molar ratio of Fe/Si and Co/Fe was synthesized by a facile hydrothermal process, and used to activate PMS for Acid Orange 7 (AO7) degradation. NaA zeolite supported Co2Fe1 with the Fe/Si molar ratio of 1:10 showed superior catalytic performance compared with other NaA zeolite supported CoxFey. In a system containing 0.6 g/L catalysts, 4 mM PMS, pH 5 and T = 30℃, 95.8% AO7 and 79.1% COD conversion could be achieved at 20 and 60 min, respectively, and the first order kinetic rate constant reached 0.14795 min-1. Moreover, NaA zeolite supported Co2Fe1/PMS system exhibited excellent catalytic effect in a wide pH range of 3-9. Temperature had an obvious effect on AO7 degradation, and the activation energy was 31.36 kJ/mol. HCO3- demonstrated an obvious depression on AO7 degradation, while Cl-, SO42- and H2PO4- had a relatively poor impact. Quenching experiments showed that both sulfate radicals ([Formula: see text]) and hydroxyl radicals (·OH) were generated in the PMS reaction system, and the [Formula: see text] was the dominant active radical. During 3 cycles experiments, an acceptable AO7 conversion ratio (91.8%) within 30 min arrived, suggesting the good stability of NaA zeolite supported Co2Fe1.

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This perspective discusses the challenges associated with the removal of cyanotoxins from raw water sources for drinking water treatment and the emergence of sulfate radical-based advanced oxidation processes (SR-AOPs) as an effective treatment technique. The advantage of SR-AOPs is that they can be activated using a variety of methods, including heat, UV radiation, and transition metal catalysts, allowing for greater flexibility in treatment design and optimization. In addition, the byproducts of SR-AOPs are less harmful than those generated by •OH-AOPs, which reduces the risk of secondary contamination. SR-AOPs generate sulfate radicals (SO4 •-) that are highly selective to certain organic contaminants and have lower reactivity to background water constituents, resulting in higher efficiency and selectivity of the process. The presence of natural organic matter and transition metals in the natural water body increases the degradation efficiency of SR-AOPs for the cyanotoxins. The bromate formation is also suppressed when the water contaminated with cyanotoxins is treated with SR-AOPs.

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Disinfection and decontamination of water by application of oxidisers is an essential treatment step across numerous industrial sectors including potable supply and industry waste management, however, could be greatly enhanced if operated as advanced oxidation processes (AOPs). AOPs destroy contaminants including pathogens by uniquely harnessing radical chemistry. Despite AOPs offer great practical opportunities, no reviews to date have highlighted the critical AOP virtues that facilitate AOPs' scale up under growing industrial demand. Hence, this review analyses the critical AOP parameters such as oxidant conversion efficiency, batch mode vs continuous-flow systems, location of radical production, radical delivery by advanced micro-/mesoporous structures and AOP process costs to assist the translation of progressing developments of AOPs into their large-scale applications. Additionally, the state of the art is analysed for various AOP inducing radical/oxidiser measurement techniques and their half-lives with a view to identify radicals/oxidisers that are suitable for in-situ production. It is concluded that radicals with short half-lives such as hydroxyl (10-4 µsec) and sulfate (30-40 µsec) need to be produced in-situ via continuous-flow reactors for their effective transport and dosing. Meanwhile, radicals/oxidisers with longer half-lives such as ozone (7-10 min), hydrogen peroxide (stable for several hours), and hypochlorous acid (10 min -17 h) need to be applied through batch reactor systems due to their relatively longer stability during transportation and dosing. Complex and costly synthesis as well as cytotoxicity of many micro-/mesoporous structures limit their use in scaling up AOPs, particularly to immobilising and delivering the short-lived hydroxyl and sulfate radicals to their point of applications. Overall, radical delivery using safe and advanced biocompatible micro-/mesoporous structures, radical conversion efficiency using advanced reactor design and portability of AOPs are priority areas of development for scaling up to industry.

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In this study, a green zero-valent iron-loaded carbon composite (ZVI-SCG) was synthesized using coffee grounds and FeCl3 solution through two-steps method, and the synthesized ZVI-SCG was used in the activation of peroxydisulfate (PDS) to degrade Levofloxacin (LEX). Results revealed that ZVI-SCG exhibited a great potential for LEX removal by adsorption and catalytic degradation in the ZVI-SCG/PDS system, and 99% of LEX was removed in the ZVI-SCG/PDS system within 60 min. ZVI-SCG/PDS system showed a high reactivity toward LEX degradation under realistic environmental conditions. Also, the ZVI-SCG/PDS system could effectively degrade several quinolone antibiotics including gatifloxacin, ciprofloxacin and LEX in single and simultaneous removal modes. A potential reaction mechanism of LEX degradation by ZVI-SCG/PDS system was proposed, SO4•-, HO•, O2•- and 1O2 involved in radical and non-radical pathways took part in catalytic degradation of LEX by ZVI-SCG/PDS system, but HO• might be the main reactive species for LEX degradation. The possible degradation pathway of LEX was also proposed based on the identified ten intermediate products, LEX degradation was successfully achieved through decarboxylation, opening ring and hydroxylation processes. The potential toxicity of LEX and its oxidation products decreased significantly after treatment. This study provides a promising strategy of water treatment for the antibiotics-containing wastewater.

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This study investigated the mechanisms of forming reactive species to degrade micropollutants through the activation of peroxymonosulfate (PMS) by phosphate, a prevalent ion in wastewater. Considering the density functional theory results, the formation of hydrogen bonds between phosphate and PMS molecules might be the crucial step in the overall reactions, which prefers producing ⋅OH and reactive phosphate species (RPS, namely H2PO4⋅, HPO4⋅-, and PO4⋅2-) to yielding SO4⋅-. Besides, in the phosphate (5 mM)/PMS system at pH = 8, HPO4⋅- was modeled to be the dominant radical with a steady-state concentration of 3.6 × 10-12 M, which was 666 and 773 times higher than those of ⋅OH and SO4⋅-. The contributions of 1O2, ⋅OH, SO4⋅-, and RPS to the micropollutant decomposition in phosphate/PMS were studied, and RPS were found to be selective for micropollutants with electron-donating moieties (such as phenolic and aniline groups). Additionally, the degradation pathways of bisphenol A, diclofenac, ibuprofen, and atrazine in phosphate/PMS were proposed according to the detected transformation products. Cytotoxicity analysis was carried out to evaluate the potential environmental impacts resulting from the degradation of micropollutants by phosphate/PMS. This study confirmed the significance of RPS for micropollutant degradation during PMS-based treatment in phosphate-rich scenarios.

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