Efficient low-strength diclofenac elimination via adsorption-concentration and peroxydisulfate activation mineralization by distinct pretreated biocarbon composites.

Sodium diclofenac (DCF) widely exists in actual water matrices, which can negatively impact ecosystems and aquatic environments even at low-strength. Herein, the adsorption-concentration-mineralization process was innovatively constructed for low-strength DCF elimination by freeze-dried biocarbon and oven-dried biocarbon coupled with cobalt oxide composites derived from the same waste biomass. Surprisingly, low-strength DCF of 0.5 mg/L was adsorbed rapidly and enriched to high-strength DCF under light with a concentration efficiency of 99.67 % by freeze-dried biocarbon. Subsequently, the concentrated DCF was economically mineralized by bifunctional oven-dried biocarbon coupled with cobalt oxide composites for peroxydisulfate (PDS) activation with full PDS activation and 76.11 % mineralization efficiency. Compared with direct low-strength DCF oxidation, adsorption-concentration-mineralization consumed less energy and none PDS residues. Mechanisms confirmed that DCF was adsorbed by freeze-dried biocarbon through hydrogen bonds and π-π stacking interactions, which were switched on due to electron-induced effect by light in DCF desorption-concentration. Furthermore, nonradical pathway (electron transfer) and radical pathway (SO4•-) were involved in efficient PDS activation by oven-dried biocarbon coupled with cobalt oxide composites for concentrated DCF mineralization, and the former was more prominent, in which graphitic carbon, cobalt redox cycle and carboxy groups were the main active sites. Overall, an energy-efficient strategy was proposed for elimination of low-strength DCF in real water matrices.

Investigation of the efficacy of graphite-sulfur iron tailing composite catalysts for activation of peroxydisulfate for rhodamine B degradation.

Herein, a novel graphite/sulfur iron tailing composite was applied as a peroxydisulfate (PDS) activator for rhodamine B (RhB) degradation in the water. The superior catalytic efficiency of graphite/sulfur iron tailing was achieved through radical (SO4•- and •OH) and non-radical (1O2) processes according to the radical quenching experiments and electron paramagnetic resonance analysis. The carbonyl group and Fe species were the main active sites on the surface of graphite/sulfur iron tailing, which was demonstrated by combining Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and reaction kinetic experiments, and a possible degradation mechanism was also proposed. Overall, activated with 0.30 g/L of C-1, PDS achieved a 94.8% removal rate for RhB and maintained a removal rate of over 85% even after five consecutive operation cycles, and this study will benefit the application of iron/carbon composite materials in practical water treatment.

Sludge-derived hydrochar modulates complete nonradical electron transfer in peroxydisulfate activation via pyrrolic-N and carbon defect: Implication for degrading electron-rich ionizable anilines compounds.

Nonradical electron transfer process (ETP) is a promising pathway for pollutant degradation in peroxydisulfate-based advanced oxidation processes (PDS-AOPs). However, there is a critical bottleneck to trigger ETP by sludge-derived hydrochar due to its negatively charged surface, inferior porosity and electrical conductivity. Herein, pyrrolic-N doped and carbon defected sludge-derived hydrochar (SDHC-N) was constructed for PDS activation to degrade anilines ionizable organic compounds (IOC) through complete nonradical ETP oxidation. Degradation of anilines IOC was not only affected by the electron-donating capacity but also proton concentration in solution because of the ionizable amino group (-NH2). Diverse effects including proton favor, insusceptible and inhibition were observed. Impressively, addition of HCO3 with strong proton binding capacity boosted aniline degradation nearly 10 times. Moreover, characterizations and theoretical calculations demonstrated that pyrrolic-N increased electron density and created positively charged surface, profoundly promoting generation of SDHC-N-S2O82-* complexes. More delocalized electrons around carbon defect could enhance electron mobility. This work guides a rational design of sludge-derived hydrochar to mediate nonradical ETP oxidation, and provides insights into the impacts of proton on anilines IOC degradation.

CuFeS2/GAC particle combined with electrochemical activation of persulfates for efficient degradation of carbamazepine.

Electrochemically activated persulfate is a potential advanced oxidation process due to its advantages of environmental friendliness, high efficiency, and convenient operation. An Fe-Cu-S granular activated carbon (CuFeS2/GAC, abbreviated as FCSG) particles electrode was developed and applied to degrade carbamazepine (CBZ) combined with electrochemical activation of persulfate (E-PDS-FCSG) in this work. Compared to two-dimensional electrochemical process (E-PDS), the three-dimensional (3D) E-PDS-FCSG process exhibited higher removal efficiency of CBZ and lower energy consumption. The removal efficiency of CBZ and power consumption increased by 96% and reduced by 67%, respectively. Over 98% of CBZ removal rate was reached within 25 min. Apart from the same free radicals in two-dimensional electrochemical process, both Fe2+ and Cu+ on the surface of three-dimensional particle electrodes can directly activate PDS to produce SO4•-, and the existence of S2- strengthens the circulation of Fe3+/Fe2+ and Cu2+/Cu+. Furthermore, FCSG particle electrode can not only directly enhance the activation of PDS, but also accelerate the electron transfer, and then effectively promoting reactive species generation. LC-MS analysis showed that the main degradation pathways of CBZ involved decarbonylation, deamination, dealkylation, ring opening and mineralization. Moreover, after five cycle experiments, over 80% of CBZ removal rate could be achieved, demonstrating that the E-PDS-FCSG system had excellent electrocatalytic performance and good stability. These findings indicate that FCSG is a promising material and could be used as a particle electrode for removing organic pollutants from water.

Analyzing the active sites of carbocatalyst for peroxydisulfate activation: Specific surface area or electrochemical surface area?

Persulfates activation by various nanomaterials has been intensively reported for advanced oxidation processes (AOPs), and substantial progress has been made in understanding the mechanism. However, most of the published articles only present the unnormalized catalytic properties, which generated confusion to compare different catalysts and identify the active sites. Herein, we presented electrochemical surface area (ECSA) as a practical normalized method and confirmed the primary active sites in N-doped graphene. By controlling the aggregation state of graphene sheets to adjust the activity of doped graphite-N species, the active sites for peroxydisulfate (PDS) activation were accurately estimated. In further experiments, specific surface area (SSA, by N2-physisorption and methylene blue adsorption) and ECSA were adopted to conclude the normalized oxidation rate constant and graphitic-N was confirmed as the primary site in nitrogen-doped graphene for the carbocatalyst/PDS system. The normalized results revealed that SSA derived from inert gas on materials could not reflect the true active sites at solid-liquid interface, while ECSA considering the operated solid-liquid situation can be used for accurate estimation of the active sites. Therefore, this study suggests that ECSA integrates the properties of both kinetics and thermodynamics, which can be adopted as a useful methodology for analyzing nano-sized environmental catalysts performance.

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.

Long-Term Stable Dispersion of Multiwalled Carbon Nanotubes by Peroxydisulfate upon Ultrasonication Activation.

Poor dispersibility of carbon nanotubes greatly hinders their practical applications. Herein, a long-term stable dispersion of multiwalled carbon nanotubes (MWCNTs) in peroxydisulfate (PDS) is achieved. MWCNTs at 40 mg L-1 are completely dispersed by PDS upon ultrasonication (US/PDS) within 64 min and a stable dispersion is maintained at least 20 days. Mechanistically, US created defects on the nanomaterial and PDS-origin free radicals attacked these defects to introduce O-containing moieties (─OH and ─COOH). Interestingly, dispersion efficiency of MWCNTs by US/PDS initially at pH 7 and 3.8 is comparable, but lower than that initially at pH 12. Both •OH and SO4 •- are produced under alkaline condition, while SO4 •- is the dominant free radicals initially at pH 7 and 3.8 during the whole dispersion period. Stronger dispersion of MWCNTs initially at pH 12 resulted from greater amounts of O-containing moieties mainly in ─OH (46.32%) rather than ─COOH (24.19%) form. This differential more strongly promotes MWCNTs-water interaction via hydrogen bonding, thereby enhancing the dispersion. Notably, no significant mass loss of MWCNTs occurred during dispersion. Overall, the developed method achieves long-term stable dispersion of MWCNTs in a manner that can significantly extend their applications.

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.

Molten salt synthesis of porous graphene-like carbons as peroxydisulfate catalyst for the efficient removal of rhodamine B dye.

Carbon materials have been receiving considerable attention as effective green catalysts for peroxydisulfate (PDS) activation to degrade organic pollutants. Herein, the porous graphene-like carbons (PGCs) were synthesized by pyrolyzing a nitrogen-rich biomass (peanut shell, PS) in the eutectic mixture of FeCl3 and ZnCl2. The results suggested that involvement of molten salts attributed the biochar the amazing properties such as high specific surface area (SBET = 2529.4 m2 g-1), abundant structural defects, high nitrogen content (6.5%), and oxygen-containing functional groups on its surface. Especially when pyrolyzed at activation temperature of 800 °C, mass ratio of 1:3:15 (PS:ZnCl2:FeCl3), and activation time of 2 h, the optimized PGCs-op exhibited outstanding performance in the catalytic degradation of rhodamine B (RhB). Almost all of RhB (99.02%) was removed in 40 min and basically not influenced by initial pH in the range of 3.00 to 9.98. Although the RhB degradation was influenced by anions (Cl-, HCO3-, HPO42-), the inhibition would be significantly alleviated within 120 min unless these substances were high in concentration. Furthermore, the quenching tests revealed that the reactive species were involved in RhB degradation in the sequence of 1O2 > O2∙- > SO4∙- > ∙OH, among which singlet oxygen played a crucial role. Combined with characterization analysis, a possible mechanism of RhB degradation in PGCs-op/PDS system was proposed. Overall, this study provided a promising metal-free catalyst for the removal of organic pollutants while achieving reutilization of the waste biomass.

Enhanced tetracycline degradation by novel Mn-FeOOH/CNNS photocatalysts in a visible-light-driven photocatalysis coupled peroxydisulfate system.

Recently, photocatalysis combined peroxydisulfate activation under visible light (PC-PDS/Vis) was developed as a promising technology for removing antibiotics in water. Herein, Mn doped FeOOH (Mn-FeOOH) nanoclusters were grown in-situ on the surface of graphitic carbon nitride nanosheets (CNNS) using a wet chemical method, which served as a visible-light-driven photocatalyst for peroxydisulfate (PDS) activation. Photovoltaic property characterizations revealed that Mn-FeOOH/CNNS owned superior light capture ability and carrier separation efficiency. According to DFT calculations, the synergistic effect between Mn and Fe species was proved to enhance the adsorption and activation of PDS. 99.7% of tetracycline (TC) was rapidly removed in 50 min in the PC-PDS/Vis system. In addition, Mn-FeOOH/CNNS exhibited high recycling stability with low iron leaching, attributed to the interaction between Mn-FeOOH clusters and carbon species. Quenching experiments and electron spin resonance (ESR) tests unveiled that •O2- played a significant role in TC removal, while •OH and SO4•- acted as additional roles contributing to the overall process. These findings given a new strategy for antibiotics degradation by photocatalysis, offering deeper insights for the advancement of sustainable and cutting-edge wastewater treatment technologies.

Activation of peroxydisulfate by zero valent iron-carbon composites prepared by carbothermal reduction: Enhanced non-radical and radical synergies.

Since its application in environmental remediation, nano zero-valent iron (nZVI) has gained wide attention for its environmental friendliness, strong reducing ability, and wide range of raw materials. However, its high preparation cost and difficulty in preservation remain the bottlenecks for their application. Carbothermal reduction is a promising method for the industrial preparation of nZVI. Micronized zero-valent iron/carbon materials (Fe0/CB) were produced in one step by co-pyrolysis of carbon and iron. The performance of the Fe0/CB is comparable to that of nZVI. In addition, Fe0/CB overcomed the disadvantages of agglomeration and oxidative deactivation of nZVI. Experiments on the Fenton-like reaction of its activated PDS showed that metronidazole (MNZ) was efficiently removed through the synergistic action of radicals and non-radicals, which were mainly superoxide radicals (·O2-), monoclinic oxygen (1O2), and high-valent iron (FeIVO). Moreover, the degradation process showed better generalization, making it suitable for a wide range of applications in the degradation of antibiotics.

Resource utilization of medical waste incineration fly ash to activate peroxydisulfate for tetracycline degradation: Synergy between adsorption and PDS activation.

Medical waste incineration fly ash (MWI FA) is classified as a hazardous solid waste. Therefore, the development of recycling technologies to convert MWI FA into useful products is necessary and challenging. In this study, we developed a sustainable approach for preparing a catalyst through the pyrolysis of water-washed MWI FA (WW FA-x, where x corresponds to the pyrolysis temperature). Subsequently, it was applied as a potent peroxydisulfate (PDS) activator to remove tetracycline (TC) from water. The results showed that the WW FA-800 exhibited remarkable adsorption performance as well as highly efficient catalytic activation of PDS, with a 115 mg/g maximum TC adsorption capacity and 93.5% (reaction kinetic rate = 315 µmol/g/h) TC removal within 60 min. A synergistic effect was achieved by adsorption and PDS activation. TC degradation was primarily driven by non-radical (1O2 and electron transfer) processes. WW FA-800 possesses multiple active sites, including defects, π-π*, O-CO groups, Fe0, and Cu(I). Three possible pathways for TC decomposition have been proposed, with the majority of intermediates exhibiting less toxicity than TC. Furthermore, the WW FA/PDS system exhibited an excellent anti-interference ability, and universality in the degradation of various organic contaminants. Notably, energy consumption was minimal, approximately 2.80 kWh/(g·TC), and the leachability of heavy metals in the WW FA-800 was within acceptable limits. This study provides a MWI FA recycling route for the development of highly active catalysts.

Peroxydisulfate-based Non-radical Oxidation of Rhodamine B by Fe-Mn Doped Granular Activated Carbon: Kinetics and Mechanism Study.

While numerous persulfate-based advanced oxidation processes (AOPs) have been studied based on fancy catalysts, the practical combination of Fe or Mn modified granular activated carbon (GAC) has seldom been investigated. The present study focused on a green and readily synthesized Fe-Mn bimetallic oxide doped GAC (Fe-Mn@GAC), to uncover its catalytic kinetics and mechanism when used in the peroxydisulfate (PDS)-based oxidation process for degrading Rhodamine B (RhB), a representative xenobiotic dye. The synthesized Fe-Mn@GAC was characterized by SEM-EDS, XRD, ICP-OES and XPS analyses to confirm its physicochemical properties. The catalytic kinetics of Fe-Mn@GAC+PDS system were evaluated under varying conditions, including PDS and catalyst dosages, solution pH, and the presence of anions. It was found Fe-Mn@GAC exhibited robust catalytic performance, being insensitive to a wide pH range from 3 to 11, and the presence of anions such as Cl-, SO4 2-, NO3 - and CO3 2-. The catalytic mechanism was investigated by EPR and quenching experiments. The results indicated the catalytic system processed a non-radical oxidation pathway, dominated by direct electron transfer between RhB and Fe-Mn@GAC, with singlet oxygen (1O2) playing a secondary role. The catalytic system also managed to maintain a RhB removal above 81 % in successive 10 cycles, and recover to 89.5 % after simple DI water rinse, showing great reusability. The catalytic system was further challenged by real dye-containing wastewater, achieving a decolorization rate of 84.5 %. This work not only provides fresh insight into the kinetics and mechanism of the Fe-Mn@GAC+PDS catalytic system, but also demonstrates its potential in the practical application in real dye-containing wastewater treatment.

Transformation of metoprolol in UV/PDS process: Role and mechanisms of degradation and polymerization.

Advanced oxidation processes for the treatment of organic pollutants in wastewater suffer from difficulties in mineralization, potential risks of dissolved residues, and high oxidant consumption. In this study, radical-initiated polymerization is dominated in an UV/peroxydisulfate (PDS) process to eliminate organic pollutant of pharmaceutical metoprolol (MTP). Compared with an ideal degradation-based UV/PDS process, the present process can save four fifths of PDS consumption at the same dissolved organic carbon removal of 47.3%. Simultaneously, organic carbon can be recovered from aqueous solution by separating solid polymers at a ratio of 50% of the initial chemical oxygen demand. The chemical structure of products was analyzed to infer the transformation pathways of MTP. Unlike previous studies on simple organic pollutants that the polymerization can occur independently, the polymerization of MTP is dependent on the partial degradation of MTP, and the main monomer in polymerization is a dominant degradation product (4-(2-methoxyethyl)-phenol, denoted as DP151). The separated solid polymers are formed by repeated oxidation and coupling of DP151 or its derivatives through a series of intermediate oligomers. This proof-of-concept study demonstrates the advantage of polymerization-dominated mechanism on dealing with large organic molecules with complex structures, as well as the potential of UV/PDS process for simultaneous organic pollution reduction and organic carbon recovery from aqueous solution.

Small concentrations, big results: µM addition of photoactive iron oxides with PMS, PDS, or H2O2, leads to enhanced removal of viruses at near-neutral pH.

The photo-Fenton process is effective for pathogen removal, and its low-cost versions can be applied in resource-poor contexts. Herein, a photo-Fenton-like system was proposed using low concentrations of iron oxides (hematite and magnetite) and persulfates (peroxymonosulfate - PMS, and peroxydisulfate - PDS), which exhibited excellent inactivation performance towards MS2 bacteriophages. In the presence of bacteria, MS2 inactivation was inhibited in H2O2 and PDS systems but promoted in PMS-involved systems. The inactivation efficacy of all the proposed systems for mixed bacteria and viruses was greater than that of the sole bacteria, showing potential practical applications. The inactivation performance of humic acid-incorporated iron oxides mediating photo-Fenton-like processes was also studied; except for the PMS-involved system, the inactivation efficacy of the H2O2- and PDS-involved systems was inhibited, but the PDS-involved system was still acceptable (< 2 h). Reactive species exploration experiments indicated that ·OH was the main radical in the H2O2 and PDS systems, whereas 1O2 played a key role in the PMS-involved system. In summary, hematite- and magnetite-mediated persulfate-assisted photo-Fenton-like systems at low concentrations can be used as alternatives to the photo-Fenton process for virus inactivation in sunny areas, providing more possibilities for point-of-use drinking water treatment in developing countries.

Electron transfer mediated photo-Fenton-like synergistic catalysis of Fe,Cu-doped MIL-101 coupled with Ag3PO4: Quantitative evaluation and DFT calculations.

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.

Comparative study on the activation of peroxymonosulfate and peroxydisulfate by Ar plasma-etching CNTs for sulfamethoxazole degradation: Efficiency and mechanisms.

Sulfamethoxazole (SMX), a widely utilized antibiotic, was continually detected in the environment, causing serious risks to aquatic ecology and water security. In this study, carbon nanotubes (CNTs) with abundant defects were developed by argon plasma-etching technology to enhance the activation of persulfate (PS, including peroxymonosulfate (PMS) and peroxydisulfate (PDS)) for SMX degradation while reducing environmental toxicity. Obviously, the increase of ID/IG value from 0.980 to 1.333 indicated that Ar plasma-etching successfully introduced rich defects into CNTs. Of note, Ar-90-CNT, whose Ar plasma-etching time was 90 min with optimum catalytic performance, exhibited a significant discrepancy between PMS activation and PDS activation. Interestingly, though the Ar-90-CNT/PDS system (kobs = 0.0332 min-1) was more efficient in SMX elimination than the Ar-90-CNT/PMS system (kobs = 0.0190 min-1), Ar plasma-etching treatment had no discernible enhancement in the catalytic efficiency of MWCNT for PDS activation. Then the discrepancy on activation mechanism between PMS and PDS was methodically investigated through quenching experiments, electron spin resonance (ESR), chemical probes, electrochemical measurements and theoretical calculations, and the findings unraveled that the created vacancy defects were the ruling active sites for the production of dominated singlet oxygen (1O2) in the Ar-90-CNT/PMS system to degrade SMX, while the electron transfer pathway (ETP), originated from PDS activation by the inherent edge defects, was the central pathway for SMX removal in the Ar-90-CNT/PDS system. Based on the toxicity test of Microcystis aeruginosa, the Ar-90-CNT/PDS system was more effective in alleviating environmental toxicity during SMX degradation. These findings not only provide insights into the discrepancy between PMS activation and PDS activation via carbon-based materials with controlled defects regulated by the plasma-etching strategy, but also efficiently degrade sulfonamide antibiotics and reduce the toxicity of their products.

Mechanisms on the removal of gram-negative/positive antibiotic resistant bacteria and inhibition of horizontal gene transfer by ferrate coupled with peroxydisulfate or peroxymonosulfate.

The existence of antibiotic resistant bacteria (ARB) and antibiotic resistance genes (ARGs) has been a global public environment and health issue. Due to the different cell structures, gram-positive/negative ARB exhibit various inactivation mechanisms in water disinfection. In this study, a gram-negative ARB Escherichia coli DH5α (E. coli DH5α) was used as a horizontal gene transfer (HGT) donor, while a gram-positive ARB Bacillus as a recipient. To develop an efficient and engineering applicable method in water disinfection, ARB and ARGs removal efficiency of Fe(VI) coupled peroxydisulfate (PDS) or peroxymonosulfate (PMS) was compared, wherein hydroxylamine (HA) was added as a reducing agent. The results indicated that Fe(VI)/PMS/HA showed higher disinfection efficiency than Fe(VI)/PDS/HA. When the concentration of each Fe(VI), PMS, HA was 0.48 mM, 5.15 log E. coli DH5α and 3.57 log Bacillus lost cultivability, while the proportion of recovered cells was 0.0017 % and 0.0566 %, respectively, and HGT was blocked. Intracellular tetA was reduced by 2.49 log. Fe(IV) and/or Fe(V) were proved to be the decisive reactive species. Due to the superiority of low cost as well as high efficiency and practicality, Fe(VI)/PMS/HA has significant application potential in ARB, ARGs removal and HGT inhibition, offering a new insight for wastewater treatment.

Fast and efficient As(III) removal from water by bifunctional nZVI@NBC.

As a notable toxic substance, metalloid arsenic (As) widely exists in water body and drinking As-contaminated water for an extended period of time can result in serious health concerns. Here, the performance of nanoscale zero-valent iron (nZVI) modified N-doped biochar (NBC) composites (nZVI@NBC) activated peroxydisulfate (PDS) for As(III) removal was investigated. The removal efficiencies of As(III) with initial concentration ranging from 50 to 1000 µg/L were above 99% (the residual total arsenic below 10 µg/L, satisfying the contaminant limit for arsenic in drinking water) within 10 min by nZVI@NBC (0.2 g/L)/PDS (100 µM). As(III) removal efficiency influenced by reaction time, PDS dosage, initial concentration, pH, co-existing ions, and natural organic matter in nZVI@NBC/PDS system were investigated. The nZVI@NBC composite is magnetic and could be conveniently collected from aqueous solutions. In practical applications, nZVI@NBC/PDS has more than 99% As(III) removal efficiency in various water bodies (such as deionized water, piped water, river water, and lake water) under optimized operation parameters. Radical quenching and EPR analysis revealed that SO4·- and ·OH play important roles in nZVI@NBC/PDS system, and the possible reaction mechanism was further proposed. These results suggest that nZVI@NBC activated peroxydisulfate may be an efficient and fast approach for the removal of water contaminated with As(III).

From rust to robust disinfectants: How do iron oxides and inorganic oxidants synergize with UVA light towards bacterial inactivation?

Pathogens in drinking water remain a challenge for human health, photo-Fenton process is a promising technique for pathogen inactivation, herein, two common iron oxides, hematite and magnetite mediate persulfate (peroxymonosulfate-PMS - and peroxydisulfate-PDS) involved photo-Fenton-like processes were constructed for E. coli inactivation, and the inactivation performance was investigated and compared with the photo-Fenton process under a low intensity UVA irradiation. Results indicated that with a low dose of iron oxides (1 mg/L) and inorganic peroxides (10 mg/L), PMS-involved photo-Fenton-like process is the best substitute for the photo-Fenton one over pH range of 5-8. In addition, humic acid (HA, one of the important components of natural organic matter) incorporated iron oxide-mediated photo-Fenton-like processes for bacteria inactivation was also studied, and facilitating effect was found in UVA/hematite/PMS and UVA/magnetite/PDS systems. Reactive oxygen species (ROS) exploration experiments revealed that ·OH was the predominant radical in H2O2- and PDS-containing systems, whereas 1O2 was one of the principal reactive species in the PMS systems. In addition to the semiconductor photocatalysis of iron oxides and UVA-activated oxidants, iron-complexes (iron-oxidant complexes and iron-bacteria complexes) mediated ligand-to-metal charge transfer (LMCT) processes also made contribution to bacterial inactivation. Overall, this study demonstrates that it is feasible to replace H2O2 with PMS in a photo-Fenton-like process for water disinfection using a low dose of reagents, mediated by cheap catalysts, such as hematite and magnetite, it is also hoped to provide some insights to practical water treatment.