In situ treatment of contaminated soil using persulfate activated by sulfidated zero-valent iron.

Soil contamination with hazardous substances like phenol poses significant environmental and health risks. In situ soil mixing can be a promising technological solution to this challenge. A persulfate and sulfidated zero-valent iron (S-ZVIbm) system for remediating contaminated soil was developed and tested to be suited to in situ soil mixing. S-ZVIbm was synthesized using a ball mill process, and the optimal sulfur to iron molar ratio for effectively removing phenol from soil removal without pyrophoric risks was 0.12. Soil slurry experiments were performed, and the best phenol oxidation results (high stoichiometric efficiency and sustained oxidation after mixing) were achieved at a persulfate to S-ZVIbm molar ratio of 2:1 and a persulfate to phenol molar ratio of 8:1. A high organic matter content of the silty clay fraction of the soil strongly suppressed persulfate activation, so suppressed phenol removal and increased persulfate consumption. Electron spin resonance and radical scavenging tests confirmed that hydroxyl and sulfate radicals were present during the degradation of phenol. While sulfate radicals predominantly facilitated degradation in the soil, both sulfate and hydroxyl radicals were crucial in the aqueous phase in the absence of soil organic matter. In situ soil mixing simulation tests indicated that the persulfate and S-ZVIbm doses and the mixing rate and duration strongly affected the efficacy of the system, and the optimal conditions for phenol removal were determined. The results indicated that the persulfate/S-ZVIbm system could be tuned to achieve sustained persulfate activation and to remediate contaminated soil employing in situ soil mixing technique.

Enhanced degradation of micropollutants using In situ electrogenerated sulfate radical at high flux.

The degradation of micropollutants via in situ-generated reactive species from coexisting substances in water is a promising approach for advanced water treatment. However, treatment efficiency and practical applications are hindered by limited operation conditions and prohibitive costs, respectively. Herein, we report an upgraded electrochemical filtration system that is chemical-free and made efficient by achieving in situ SO4•- generation at enhanced flux and in complicated water matrices. The ion transport was enhanced by coupled electric and flow fields, providing an outstanding performance in removing micropollutants. At the optimized conditions, the proposed system degraded 90.5% of bisphenol A (BPA) in 40 min and its degradation kinetics was 14.7 times that of the batch mode, and the treatment efficiency of the proposed system was 2.5 times more efficient than our previous design because of the enhanced flux. Quenching experiments indicate that indirect oxidation by SO4•- and •OH as well as direct electron transfer play critical roles during the BPA degradation. Importantly, the proposed system does not need any added chemicals and uses only the ubiquitous SO42- and electricity. From an environmental point of view, its energy conservation and the lack of additional chemicals ensure its applicability for purifying micropollutants.

Deciphering the Formation of Fe(IV) in the Fe(II)/Peroxydisulfate Process: The Critical Role of Sulfate Radical.

This study delves into the formation of ferryl ions (Fe(IV)) within the Fe(II)/peroxydisulfate (PDS) process, a pivotal reaction in advanced oxidation processes (AOPs) aimed at organic pollutant removal. Our findings challenge the conventional view that Fe(IV) predominantly forms through oxygen transfer from PDS to Fe(II), revealing that sulfate radicals (SO4•-) play a crucial role in Fe(IV) generation. By employing competitive kinetics, the second-order rate constant for Fe(III) oxidation by SO4•- was quantified as 4.58 × 108 M-1 s-1. Factors such as the probe compound concentration, chloride presence, and iron species influence Fe(IV) generation, all of which were systematically evaluated. Additionally, the study explores Fe(IV) formation in various Fe(II)-activated AOPs, demonstrating that precursors like peroxymonosulfate and H2O2 can also directly oxidize Fe(II) to Fe(IV). Through experimental data, kinetic modeling, and oxygen-18 labeling experiments, this research offers a comprehensive understanding of the Fe(II)/PDS system, facilitating the optimization of AOPs for pollutant degradation. Finally, introducing HSO3- was proposed to shift the Fe(II)/PDS process from Fe(IV)-dominated to SO4•--dominated mechanisms, thereby enhancing pollutant removal efficiencies.

Efficient degradation and mineralization of polyethylene terephthalate microplastics by the synergy of sulfate and hydroxyl radicals in a heterogeneous electro-Fenton-activated persulfate oxidation system.

The presence of polyethylene terephthalate (PET) microplastics (MPs) in waters has posed considerable threats to the environment and humans. In this work, a heterogeneous electro-Fenton-activated persulfate oxidation system with the FeS2-modified carbon felt as the cathode (abbreviated as EF-SR) was proposed for the efficient degradation of PET MPs. The results showed that i) the EF-SR system removed 91.3 ± 0.9 % of 100 mg/L PET after 12 h at the expense of trace loss (< 0.07 %) of [Fe] and that ii) dissolved organics and nanoplastics were first formed and accumulated and then quickly consumed in the EF-SR system. In addition to the destruction of the surface morphology, considerable changes in the surface structure of PET were noted after EF-SR treatment. On top of the emergence of the O-H bond, the ratio of C-O/C=O to C-C increased from 0.25 to 0.35, proving the rupture of the backbone of PET and the formation of oxygen-containing groups on the PET surface. With the verified involvement and contributions of SO4•- and •OH, three possible paths were proposed to describe the degradation of PET towards complete mineralization through chain cleavage and oxidation in the EF-SR system.

Magnetic raspberry-like CuCo nanoalloy-embedded carbon as an enhanced activator of Oxone to degrade azo contaminant: Cu-induced hollowed structure and boosted activities.

Azo compounds, particularly azo dyes, are widely used but pose significant environmental risks due to their persistence and potential to form carcinogenic by-products. Advanced oxidation processes (AOPs) are effective in degrading these stubborn compounds, with Oxone activation being a particularly promising method. In this study, a unique nanohybrid material, raspberry-like CuCo alloy embedded carbon (RCCC), is facilely fabricated using CuCo-glycerate (Gly) as a template. With the incorporation of Cu into Co, RCCC is essentially different from its analogue derived from Co-Gly in the absence of Cu, affording a popcorn-like Co embedded on carbon (PCoC). RCCC exhibits a unique morphology, featuring a hollow spherical layer covered by nanoscale beads composed of CuCo alloy distributed over carbon. Therefore, RCCC significantly outperforms PCoC and Co3O4 for activating Oxone to degrade the toxic azo contaminant, Azorubin S (AS), in terms of efficiency and kinetics. Furthermore, RCCC remains highly effective in environments with high NaCl concentrations and can be efficiently reused across multiple cycles. Besides, RCCC also leads to the considerably lower Ea of AS degradation than the reported Ea values by other catalysts. More importantly, the contribution of incorporating Cu with Co as CuCo alloy in RCCC is also elucidated using the Density-Function-Theory (DFT) calculation and synergetic effect of Cu and Co in CuCo contributes to enhance Oxone activation, and boosts generation of SO4•-and •OH. The decomposition pathway of AS by RCCC + Oxone is also comprehensively investigated by studying the Fukui indices of AS and a series of its degradation by-products using the DFT calculation. In accordance to the toxicity assessment, RCCC + Oxone also considerably reduces acute and chronic toxicities to lower potential environmental impact. These results ensure that RCCC would be an advantageous catalyst for Oxone activation to degrade AS in water.

Regulation of reactive species during ionizing radiation by peroxydisulfate for enhanced degradation of typical pollutants in coking wastewater.

This study focused on exploring the effect of peroxydisulfate (PDS) on the regulation of reactive species during water radiolysis process and its potential application for degrading organic pollutants. The results indicated that PDS was successfully activated by ionizing radiation for efficient removal of three typical phenolic compounds over a wide pH range (3.0∼12.0) at absorbed dose of 5 kGy. Chemical probe methods provided the evidence that the addition of PDS could introduce the sulfate radicals (SO4•-) and enhance the production of hydroxyl radicals (•OH). According to the quenching tests, •OH and SO4•- were the dominant reactive species responsible for the degradation of 4-NP, while hydrated electron (eaq-) played a minor role. The regulatory effect of PDS on active species in the ionizing radiation process could divided by (i) PDS could be directly activated by ionizing radiation to produce •OH and SO4•- via energy transfer pathway; (ii) PDS could boost the conversion of eaq- to SO4•- via electron transfer pathway. Furthermore, we assessed the applicability of the IR and IR/PDS systems in treating mixed solutions containing various pollutants and actual coking wastewater.

A review on recent advancements in the treatment of polyaromatic hydrocarbons (PAHs) using sulfate radicals based advanced oxidation process.

Polyaromatic hydrocarbons (PAHs) are the most persistent compounds that get contaminated in the soil and water. Nearly 16 PAHs was considered to be a very toxic according US protection Agency. Though its concentration level is low in the environments but the effects due to it, is enormous. Advanced Oxidation Process (AOP) is an emergent methodology towards treating such pollutants with low and high molecular weight of complex substances. In this study, sulfate radical (SO4‾•) based AOP is emphasized for purging PAH from different sources. This review essentially concentrated on the mechanism of SO4‾• for the remediation of pollutants from different sources and the effects caused due to these pollutants in the environment was reduced by this mechanism is revealed in this review. It also talks about the SO4‾• precursors like Peroxymonosulfate (PMS) and Persulfate (PS) and their active participation in treating the different sources of toxic pollutants. Though PS and PMS is used for removing different contaminants, the degradation of PAH due to SO4‾• was presented particularly. The hydroxyl radical (•OH) mechanism-based methods are also emphasized in this review along with their limitations. In addition to that, different activation methods of PS and PMS were discussed which highlighted the performance of transition metals in activation. Also this review opened up about the degradation efficiency of contaminants, which was mostly higher than 90% where transition metals were used for activation. Especially, on usage of nanoparticles even 100% of degradation could be able to achieve was clearly showed in this literature study. This study mainly proposed the treatment of PAH present in the soil and water using SO4‾• with different activation methodologies. Particularly, it emphasized about the importance of treating the PAH to overcome the risk associated with the environment and humans due to its contamination.

Efficiency of ozonation and sulfate radical - AOP for removal of pharmaceuticals, corrosion inhibitors, x-ray contrast media and perfluorinated compounds from reverse osmosis concentrates.

This study investigated the elimination of pharmaceuticals, corrosion inhibitors, x-ray contrast media and perfluorinated compounds from reverse osmosis concentrates during ozonation and UV/persulfate processes. Second-order rate constants for the reactions of candesartan, irbesartan, methyl-benzotriazole, and chloro­benzotriazole with sulfate radical (SO4·-) were determined for the first time. Experiments were conducted in buffered pure water, in buffered water added with the matrix substituents chloride, carbonate, NOM, and reverse osmosis concentrate with spiked micropollutants (MP). UV/persulfate eliminated all MP to a higher extent than ozonation in RO concentrates due to the higher yield of oxidative species and photolytic degradation. Compounds with electron-rich moieties such as carbamazepine, diclofenac, metoprolol, and sulfamethoxazole were completely eliminated with small ozone doses (< 0.5 mg O3 / mg DOC) and with a small fluence (< 5000 J m-2) in UV/persulfate processes. Photosensitive compounds with high reactivity towards hydroxyl radicals (·OH) and SO4·- like the x-ray contrast media Iopamidol, Iohexol, and Amidotrizoic acid were successfully eliminated with a reasonable fluence in UV/persulfate, whereas these compounds persist in ozonation at common ozone dosages. However, much higher fluences and ozone dosages were required for the least reactive compounds like the class of benzotriazoles. Comparing the application of both oxidative processes to the RO concentrate, ozonation has the disadvantage of forming bromate. The energy input of both processes strongly depends on the target compounds to be eliminated. For the elimination of compounds such as sulfamethoxazole, ozonation is a feasible technique, whereas UV/persulfate is better suited for the elimination of recalcitrant compounds such as x-ray contrast media. In general, oxidative process treatment of RO concentrate could be applied to partly abate micropollutants before discharge.

Formation of nitrated naphthalene in the sulfate radical oxidation process in the presence of nitrite.

Polycyclic aromatic hydrocarbons (PAHs) have become a global environmental concern due to their potential hazardous implication for human health. In this study, we found that sulfate radical (SO4•-) could effectively degrade naphthalene (NAP), a representative PAH in groundwaters, generating 1-naphthol. This intermediate underwent further degradation, yielding ring-opening products including phthalic acid and salicylic acid. However, the presence of nitrite (NO2-), a prevalent ion in subsurface environments, was observed to compete with NAP for SO4•-, thus slowing down the NAP degradation. The reaction between NO2- and SO4•- generated a nitrogen dioxide radical (NO2•). Concurrently, in-situ formed 1-naphthol underwent further oxidization to the 1-naphthoxyl radical by SO4•-. The coupling of 1-naphthoxyl radicals with NO2• gave rise to a series of nitrated NAP, namely 2-nitro-1-naphthol, 4-nitro-1-naphthol, and 2,4-dinitro-1-naphthol. In addition, the in-situ formed phthalic acid and salicylic acid also underwent nitration, generating nitrophenolic products, although this pathway appeared less prominent than the nitration of 1-naphthol. When 10 µΜ NAP was subjected to heat activated peroxydisulfate oxidation in the presence of 10 µΜ NO2-, the total yield of nitrated products reached 0.730 µΜ in 120 min. Overall, the presence of NO2- dramatically altered the behavior of NAP degradation by SO4•- oxidation and contributed to the formation of toxic nitrated products. These findings raise awareness of the potential environmental risks associated with the application of SO4•--based oxidation processes for the remediation of PAHs-polluted sites in presence of NO2-.

Olive mill wastewater treatment strategies to obtain quality water for irrigation: A review.

The olive mill industry is a relevant sector in the economy of Mediterranean countries, while it involves high consumption of water and the production of effluents with high environmental impact. The efficient treatment of olive mill wastewater (OMW) is of high relevance, particularly for these countries. Climate changes are leading to increasing periods of droughts, and water recovery from polluted streams is essential to ensure the sustainability of this scarce resource. A combination of various technologies involving physical, chemical, and biological processes has been developed for OMW treatment. However, the treatments studied have limitations such as the operation costs, difficulty of industrial scale-up, and the fact that the vast majority do not lead to suitable treated water for discharge/reuse. As such, it is urgent to develop a solution capable of efficiently treating this effluent, overcoming the disadvantages of existing processes to convert OMW from a serious environmental problem into a valuable source of water and nutrients. In this review, several studies based on the OMW treatment are critically discussed, from conventional approaches such as the physical (e.g. centrifugation, filtration, and adsorption) and biological (anaerobic digestion and anaerobic co-digestion) processes, to the most recent technologies such as advanced membrane filtration, advanced oxidation processes (AOPs) and sulfate radical based AOPs (SR-AOPs). Due to the complexity of the effluent, OMW cannot be efficiently treated by a single process, requiring a sequence of technologies before reaching the required characteristics for discharge into water courses or use in crop irrigation. Reviewing the published results in this matter, it seems that the sequence of processes encompassing ozonation, anaerobic digestion, and SR-AOPs could be the ideal combination for this purpose. However, membrane technologies may be necessary in the final stage of treatment so that the effluent meets legal discharge or irrigation limits.

Research Progress of Ozone/Peroxymonosulfate Advanced Oxidation Technology for Degrading Antibiotics in Drinking Water and Wastewater Effluent: A Review.

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.

Oxidative Transformation of Nafion-Related Fluorinated Ether Sulfonates: Comparison with Legacy PFAS Structures and Opportunities of Acidic Persulfate Digestion for PFAS Precursor Analysis.

The total oxidizable precursor (TOP) assay has been extensively used for detecting PFAS pollutants that do not have analytical standards. It uses hydroxyl radicals (HO•) from the heat activation of persulfate under alkaline pH to convert H-containing precursors to perfluoroalkyl carboxylates (PFCAs) for target analysis. However, the current TOP assay oxidation method does not apply to emerging PFAS because (i) many structures do not contain C-H bonds for HO• attack and (ii) the transformation products are not necessarily PFCAs. In this study, we explored the use of classic acidic persulfate digestion, which generates sulfate radicals (SO4-•), to extend the capability of the TOP assay. We examined the oxidation of Nafion-related ether sulfonates that contain C-H or -COO-, characterized the oxidation products, and quantified the F atom balance. The SO4-• oxidation greatly expanded the scope of oxidizable precursors. The transformation was initiated by decarboxylation, followed by various spontaneous steps, such as HF elimination and ester hydrolysis. We further compared the oxidation of legacy fluorotelomers using SO4-• versus HO•. The results suggest novel product distribution patterns, depending on the functional group and oxidant dose. The general trends and strategies were also validated by analyzing a mixture of 100000- or 10000-fold diluted aqueous film-forming foam (containing various fluorotelomer surfactants and organics) and a spiked Nafion precursor. Therefore, (1) the combined use of SO4-• and HO• oxidation, (2) the expanded list of standard chemicals, and (3) further elucidation of SO4-• oxidation mechanisms will provide more critical information to probe emerging PFAS pollutants.

Sulfate radical dominated rapid pollutants degradation leaded by selenium vacancies in core-shell N-doped carbon wrapped cobalt diselenide nanospheres.

Herein, a new heterogeneous CoSe2-x@NC material with abundant selenium vacancies is synthesized via an in-situ carbonization-selenization process from cobaltic metal organic framework (Co-MOF). The obtained CoSe2-x@NC has a unique electronic structure and rich active sites, which can activate peroxymonosulfate (PMS) to degrade carbamazepine (CBZ) with superior catalytic performance and stability. The quenchingexperiments and EPR test show that SO4•- is the dominant reactive oxidation species (ROSs) for CBZ degradation. Significantly, systemic electrochemical tests and theoretical calculations illustrated that the dominant role of SO4•- is attributed to the existence of abundant selenium vacancies in CoSe2-x@NC, which can adjust the density of electron cloud of the Co atoms in CoSe2-x@NC to improve the PMS adsorption and promoting the conversion of transition metallic redox pairs (Co3+/Co2+). This work provides a facile way to improve the activity and stability of CoSe2 by defect engineering in the PMS based advanced oxidation process (AOPs).

Advances and challenges in the removal of organic pollutants via sulfate radical-based advanced oxidation processes by Fe-based metal-organic frameworks: A review.

Organic contaminants, notorious for their complexity and resistance to degradation, are prevalent in aquatic environments, posing severe threats to ecosystems. Sulfate radical-based advanced oxidation processes (SR-AOPs), known for their stability and high effectiveness, have become a common choice for treating organic wastewater. Metal-organic framework materials (MOFs) have garnered substantial attention due to their facile chemical manipulation, unique structural configurations, and other favorable properties. Therefore, this article critically reviews recent advances in research involving the utilization of Fe-based MOFs (Fe-MOFs) and their derivatives in SR-AOPs. Specifically, it highlights the manipulation of influencing factors within the system to enhance the degradation of organic pollutants. The mechanisms and applications underlying the degradation of organic pollutants in the SR-AOPs system are also elucidated.

Reinvestigation on High-Valent Cobalt for the Degradation of Micropollutants in the Co(II)/Peroxymonosulfate System: Roles of Co(III).

Recently, reactive cobalt (Co) species, including Co(IV)-oxo and Co(II)-OOSO3- complexes, were proposed to be the primary intermediates formed during the process of activating peroxymonosulfate (PMS) by Co(II), mainly based on the observation that the methyl phenyl sulfoxide (MPSO) probe was transformed to methyl phenyl sulfone (MPSO2) in this process. However, in this work, we rationalized the results of the MPSO probe assay based on the chemistry of aqueous Co(III), an alternative reactive Co species. Moreover, 18O-labeled water experiments and Raman spectroscopy analysis clearly proved the Co(III) formation in the Co(II)/PMS system. In parallel, sulfate radicals (SO4•-) and hydroxyl radicals (HO•) were also involved in this system. Further, the relative contribution of Co(III) to the abatement of carbamazepine (CBZ), a representative micropollutant, in the Co(II)/PMS system was significantly increased by increasing the Co(II) dosage but was dramatically decreased by improving the PMS dosage and increasing the pH from 3 to 7. Additionally, the degradation pathway of CBZ by Co(III) and the Co(II)/PMS system was comparatively explored, confirming that Co(III) participated in the hydroxylation, carbonylation, deacetylation, and ring reduction of CBZ by the Co(II)/PMS system. Our work addresses the controversy regarding the reactive Co species involved in the Co(II)/PMS system with evidence of Co(III) as the chief one, which highlights the significance of re-evaluating the relative contribution of Co(III) in relevant environmental decontamination processes.

Oxidation of emerging contaminants by S(IV) activated ferrate: Identification of reactive species.

Studies on the Fe(VI)/S(IV) process have focused on improving the efficiency of emerging contaminants (ECs) degradation under alkaline conditions. However, the performance and mechanisms under varying pH levels remain insufficiently investigated. This tudy delved into the efficiency and mechanism of Fe(VI)/S(IV) process using sulfamethoxazole (SMX) and ibuprofen (IBU) as model contaminants. We found that pH was crucial in governing the generation of reactive species, and both Fe(V/IV) and SO4•- were identified in the reaction system. Specifically, an increase in pH favored the formation of SO4•-, while the formation of Fe(VI) to Fe(V/IV) became more significant at lower pH. At pH 3.2, Fe(III) resulting from the Fe(VI) self-decay reactedwith HSO3-to produce SO4•-and •OH. Under near-neutral conditions, the coexistance of Fe(V/IV) and SO4•- in abundance contributed to the optimal oxidation of both pollutants in the Fe(VI)/S(IV) process, with the removal exceeding 74% in 5 min. Competitive quenching experiments showed that the contributions of Fe(V/IV) to SMX and IBU destruction dimished, while the contributions of radicals increased with an increase in pH. However, this evolution was slower during SMX degradation compared to IBU degradation. A comprehensive understnding of pH as the key factor is essential for the optimization of the sulfite-activated Fe(VI) oxidation process in water treatment.

Solar-driven persulfate degradation of caffeine and cephradine in synthetic human urine.

Urine source separation, as an innovative concept for the reuse of microlevel nutrients in human urine, has drawn increasing attention recently. Consequently, removing coexisting pharmaceuticals in urine is necessary for further reuse. This study is the first to apply the solar-driven persulfate process (Solar/PS) to the investigation of cephradine (CFD) and caffeine (CAF) degradation in synthetic human urine. The results showed that significantly more degradation of CFD and CAF occurs with the Solar/PS process than with persulfate oxidation and direct sunlight photolysis, respectively. The generated reactive species ·OH, SO4·-, O2·- and 1O2 were identified in the Solar/PS process. While SO4·- played a dominant role at pH 6, it played a minor role at pH 9 due to the lower amount generated under alkaline conditions. The presence of chloride and ammonia negatively impacted the photodegradation of both compounds. In contrast, bicarbonate exhibited no effect on CAF but enhanced CFD degradation owing to its amino-acid-like structure, which has a higher reactivity toward CO3·-. Although total organic carbon (TOC) was partially mineralized after 6 h of operation, no Microtox® toxicity was observed.

Cobalt doping amount determines dominant reactive species in peroxymonosulfate activation via porous carbon catalysts co-doped by cobalt and nitrogen.

Switching the reaction routes in peroxymonosulfate (PMS)-based advanced oxidation processes have attracted much attention but remain challenging. Herein, a series of Co-N/C catalysts with different compositions and structures were prepared by using bimetallic zeolitic imidazolate frameworks based on ZIF-8 and ZIF-67 (xZn/Co-ZIFs). Results show that Co doping amount could mediate the transformation of the activation pathway of PMS over Co-N/C. When Co doping amount was less than 10%, the constructed xCo-N/C/PMS system (x ≤ 10%) was singlet oxygen-dominated reaction; however further increasing Co doping amount would lead to the generation and coexistence of sulfate radicals and high-valent cobalt, besides singlet oxygen. Furthermore, the nitrogen-coordinated Co (Co-NX) sites could serve as main catalytically active sites to generate singlet oxygen. While excess Co doping amount caused the formation of Co nanoparticles from which leached Co ions were responsible for the generation of sulfate radicals and high-valent cobalt. Compared to undoped N/C, Co doping could significantly enhance the catalytic performance. The 0.5% Co-N/C could achieve the optimum degradation (0.488 min-1) and mineralization abilities (78.4%) of sulfamethoxazole among the investigated Co-N/C catalysts, which was superior to most of previously reported catalysts. In addition, the application prospects of the two systems in different environmental scenarios (pH, inorganic anions and natural organic matter) were assessed and showed different degradation behaviors. This study provides a strategy to regulate the reactive species in PMS-based advanced oxidation process.

Degradation of Ciprofloxacin in Water by Magnetic-Graphene-Oxide-Activated Peroxymonosulfate.

Antibiotics are extensively applied in the pharmaceutical industry, while posing a tremendous hazard to the ecosystem and human health. In this study, the degradation performance of ciprofloxacin (CIP), one of the typical contaminants of antibiotics, in an oxidation system of peroxymonosulfate (PMS) activated by magnetic graphene oxide (MGO) was investigated. The effects of the MGO dosage, PMS concentration and pH on the degradation of CIP were evaluated, and under the optimal treatment conditions, the CIP degradation rate was up to 96.5% with a TOC removal rate of 63.4%. A kinetic model of pseudo-secondary adsorption indicated that it involves an adsorption process with progressively intensified chemical reactions. Furthermore, the MGO exhibited excellent recyclability and stability, maintaining strong catalytic activity after three regenerative cycles, with a CIP removal rate of 87.0%. EPR and LC-MS experiments suggested that •OH and SO4-• generated in the MGO/PMS system served as the main reactants contributing to the decomposition of the CIP, whereby the CIP molecule was effectively destroyed to produce other organic intermediates. Results of this study indicate that organic pollutants in the aqueous environment can be effectively removed in the MGO/PMS system, in which MGO has excellent catalytic activity and stabilization for being recycled to avoid secondary pollution, with definite research value and application prospects in the field of water treatment.

[Bisulfite Promoted Minute Fe2+-Activated Peroxydisulfate for Paracetamol Degradation].

Fe2+ has been commonly selected to activate peroxydisulfate(PDS) for sulfate radical(SO4-·) generation because of its eco-friendly, cost-effective, and high activity characteristics. However, Fe2+ can be rapidly oxidized to Fe3+ in the reaction, leading to poor utilization of iron for PDS activation. Further, a fairly high concentration of Fe2+ is generally required and may cause iron sludge production and secondary pollution. In this study, a minute Fe2+-activated PDS system induced by bisulfite(BS) was used to degrade paracetamol(APAP) in water. The results showed that the Fe2+-PDS system could be enhanced by the circulation of Fe2+-Fe3+ with the injection of BS and by keeping Fe2+ at a high concentration. Under the optimal conditions(PDS=0.6 mol·L-1; BS=0.4 mol·L-1; Fe2+=10 µmol·L-1; pH=4), 100% APAP(4 µmol·L-1) was removed within 180 s. The degradation rate of APAP increased with the increase in BS(0-0.6 mmol·L-1) and PDS(0.2-1.5 mmol·L-1) concentration, and a modest Fe2+ concentration could accelerate APAP removal. Co-existing substances inhibited the APAP removal and followed the order of HCO3->HPO42->Cl->NO3->humic acid(HA). Based on the quenching experiments and electron paramagnetic resonance spectroscopy test, SO4-· was shown to be the primary reactive species for APAP decomposition in the BS-Fe2+-PDS process. Three-dimensional fluorescence spectroscopy revealed that APAP intermediates had fluorescence characteristics. Moreover, five intermediates were identified, and the probable APAP degradation pathways were proposed. The removal efficiencies of APAP were lower in real waters than that in ultrapure water. Nevertheless, the removal effect was greatly improved after a prolonged reaction time. All results indicated that the BS-Fe2+-PDS system could be a promising method for organic pollutant treatment.