A granular adsorbent-supported Fe/Ni nanoparticles activating persulfate system for simultaneous adsorption and degradation of ciprofloxacin

In this work,Fe/Ni nanoparticles were produced through Fe(II)and Ni(II)reduction by NaBH4 and they were stabilized by a kind of prepared granular adsorbent(Fe/Ni@PGA).Fe/Ni@PGA as an environment-friendly activator was used to activate persulfate(PS)for the removal of ciprofloxacin from aqueous solution.Fe/Ni@PGA was systematically characterized via Brunauer-Emmett-Teller(BET)method,X-ray diffraction(XRD),scanning electron microscopy(SEM),and Fourier transform infrared spectroscopy(FTIR).The effects of PS concentration,initial solution pH,Fe/Ni@PGA dosage,initial ciprofloxacin concentration,reaction temperature,anions,and natural organic matters on the removal of ciprofloxacin by Fe/Ni@PGA/PS were analyzed.The removal efficiency of ciprofloxacin by Fe/Ni@PGA/PS was 93.24%under an initial pH of 3.0,PS concentration of 10 mM,Fe/Ni@PGA dosage of 0.1 g,and reaction temperature of 30℃.Fe/Ni@PGA could still exhibit high catalytic activity after nine cycles of regeneration.The removal mechanisms for ciprofloxacin by the Fe/Ni@PGA/PS system were proposed.In summary,the Fe/Ni@PGA/PS system could be applied as a promising technology for ciprofloxacin removal.

Factors hindering the degradation of pharmaceuticals from human urine in an iron-activated persulfate system

This study investigated the degradation of clofibric acid(CFA),bezafibrate(BZF),and sulfamethoxazole(SMX)in synthetic human urine using a novel mesoporous iron powderactivated persulfate system(mFe-PS system),and identified the factors limiting their degradation in synthetic human urine.A kinetic model was established to expose the radical production in various reaction conditions,and experiments were conducted to verify the modeling results.In the phosphate-containing mFe-PS system,the 120 min removal efficiency of CFA decreased from 95.1%to 76.6%as the phosphate concentration increased from 0.32 to 6.45 mmol/L,but recovered to 90.5%when phosphate concentration increased to 16.10 mmol/L.Meanwhile,the increased concentration of phosphate from 0.32 to 16.10mmol/L reduced the BZF degradation efficacy from 91.5%to 79.0%,whereas SMX removal improved from 37.3%to 62.9%.The m Fe-PS system containing(bi)carbonate,from 4.20 to166.70 mmol/L,reduced CFA and BZF removal efficiencies from 100%to 76.8%and 80.4%,respectively,and SMX from 83.5%to 56.7%within a 120-min reaction time.In addition,alkaline conditions(pH≥8.0)inhibited CFA and BZF degradations,while nonacidic pH(pH≥7.0)remarkably inhibited SMX degradation.Results of the kinetic model indicated the formation of phosphate(H_(2)PO_(4)^(·)/HPO_(4)^(·-))and/or carbonate radicals(CO_(3)^(·-))could limit pharmaceutical removal.The transformation products(TPs)of the pharmaceuticals revealed more incompletely oxidized TPs occurred in the phosphate-and(bi)carbonate-containing m Fe-PS systems,and indicated that H_(2)PO_(4)^(·)/HPO_(4)^(·-)mainly degraded pharmaceuticals via a benzene ring-opening reaction while CO_(3)^(·-)preferentially oxidized pharmaceuticals via a hydroxylation reaction.

Achieving high-efficient photocatalytic persulfate-activated degradation of tetracycline via carbon dots modified MIL-101(Fe)octahedrons

The synergistic reaction of photocatalysis and advanced oxidation is a valid strategy for the degradation of harmful antibiotic wastewater.Herein,carbon dots(CDs)modified MIL-101(Fe)octahedrons to form CDs/MIL-101(Fe)composite photocatalyst was synthesized for visible light-driven photocatalytic/persulfate(PS)-activated tetracycline(TC)degradation.The electron spin resonance(ESR)spectra,scavenging experiment and electrochemical analysis were carried out to reveal that the high visible light-driven photocatalytic degradation activity of TC over CDs/MIL-101(Fe)photocatalysts is not only ascribed to the production of free active radicals in the CDs/MIL-101(Fe)/PS system(·OH,·SO_(4-),^(1)O_(2),h^(+)and·O_(2)^(-))but also attributed to the consumption of electrons caused by the PS,which can suppress the recombination of photo-generated carriers as well as strong light scattering and electron trapping effects of CDs.Finally,the possible degradation pathways were proposed by analyzing intermediates via liquid chromatography-mass spectrometry technique.This research presents a rational design conception to construct a CDs/PS-based photocatalysis/advanced oxidation technology with high-efficient degradation activity for the remediation of organic antibiotic pollutant wastewater and for the improvement of carrier transport kinetics of photocatalysts.

A novel graphene oxide-carbon nanotubes anchored α-FeOOH hybrid activated persulfate system for enhanced degradation of Orange Ⅱ

Persulfate activation has been applied as one of the efficient advanced oxidation processes(AOPs) to remediate polluted environments. In this study, a novel α-FeOOH anchored by graphene oxide(GO)-carbon nanotubes(CNTs) aerogel(α-FeOOH@GCA) nanocomposite activated persulfate system(α-FeOOH@GCA + K2S2O8) was applied for decolorization of Orange Ⅱ(OⅡ). The decolorization of OⅡ was remarkably enhanced to a level of ~ 99% in this system compared with that of pristine α-FeOOH(~ 44%) or GO-CNTs(~18%). The enhanced catalytic activity of α-FeOOH@GCA was due to the formation of a heterojunction byα-FeOOH and GO-CNTs as confirmed by the presence of Fe–O–C chemical bonds. The degradation intermediates of OⅡ were comprehensively identified. The proposed degradation pathway of OⅡ begins with the destruction of the conjugated structures of OⅡ by the dominant reactive oxygen species, surface-bound SO4·-. The decolorization efficiency of OⅡ by the α-FeOOH@GCA activated persulfate system decreased from the first to third cycle of recycling. Ultraviolet(UV) irradiation or introduction of a small amount of Fe2+ could restore the activation of this system. The results show that the α-FeOOH@GCA persulfate activation system promises to be a highly efficient environmental remediation method for organic pollutants.

New insights into FeS/persulfate system for tetracycline elimination:Iron valence,homogeneous-heterogeneous reactions and degradation pathways

In this study,complete tetracycline(TTC)and above 50%of total organic carbon(TOC)were removed by Fe S/PS after 30 min under optimized conditions.Although free radicals and high-valent iron ions were identified to generate in the process,the apparent similarity between intermediate products of Fe S/PS,Fe/PS,and UV/PS systems demonstrated that the degradation of TTC was due to sulfate radicals(SO_(4)·^(-))and hydroxyl radicals(·OH).Based on the reaction between free radicals and organic matter,we speculated that TTC in the Fe S/PS system was decomposed and mineralized by dehydration,dehydrogenation,hydroxyl addition,demethylation,substitution,E-transfer,and ring-opening.Furthermore,a new understanding of Fe S-mediated PS activation based on stoichiometry and kinetic analysis showed that there were both homogeneous and heterogeneous reactions that occurred in the entire progress.However,due to the effect of p H on the dissolution of iron ions,the homogeneous reaction became the principal process with iron ions concentration exceeding 1.35 mg/L.This work provides a theoretical basis for the study of the degradation of TTC-containing wastewater by the iron-based advanced oxidation process.

Leaching of a copper flotation concentrate with ammonium persulfate in an autoclave system

The leaching behavior of a copper flotation concentrate was investigated using ammonium persulfate （APS） in an autoclave systee. The decomposition products of APS, active oxygen, and acidic medium were used to extract metals from the concentrate. Leaching experiments were performed to compare the availability of APS as an oxidizing agent for leaching of the concentrate under atmospheric conditions and in an autoclave system. Leaching temperature and APS concentration were found to be important parameters in both leaching systems. Atmospheric leaching studies showed that the metal extractions increased with the increase in APS concentration and temperature （up to 333 K）. A similar tendency was determined in the autoclave studies up to 423 K. It was also determined that the metal extractions decreased at temperatures above 423 K due to the passivation of the particle surface by molten elemental sulfur. The results showed that higher copper extractions could be achieved using an autoclave system.

Degradation of carbon tetrachloride in thermally activated persulfate system in the presence of formic acid

The thermally activated persulfate （PS） degradation of carbon tetrachloride （CT） in the presence of formic acid （FA） was investigated. The results indicated that CT degradation followed a zero order kinetic model, and CO2^- was responsible for the degradation of CT confirmed by radical scavenger tests. CT degradation rate increased with increasing PS or FA dosage, and the initial CT had no effect on CT degradation rate. However, the initial solution pH had effect on the degradation of CT, and the best CT degradation occurred at initial pH 6. Cl^- had a negative effect on CT degradation, and high concentration of Cl^- displayed much strong inhibition. Ten mmol·L^-1HCO3^- promoted CT degradation, while 100mmol·L^-1NO3^- inhibited the degradation of CT, but SO4^2- promoted CT degradation in the presence of FA. The measured Cl^- concentration released into solution along with CT degradation was 75.8% of the total theoretical dechlorination yield, but no chlorinated intermediates were detected. The split of C-Cl was proposed as the possible reaction pathways in CT degradation. In conclusion, this study strongly demonstrated that the thermally activated PS system in the presence of FA is a promising technique in in situ chemical oxidation （ISCO） remediation for CT contaminated site.

Degradation of benzene derivatives in the CuMgFe-LDO/persulfate system:The role of the interaction between the catalyst and target pollutants

A novel insight on the role of interactions between target pollutants and the catalyst in the copper-containing layered double oxide(LDO)-catalyzed persulfate(PS)system was elucidated in the present study.4-Chlorophenol(4-CP),as a representative benzene derivative with a hydroxyl group,was completely removed within 5 min,which was much faster than the reaction of monochlorobenzene(MCB)without a hydroxyl group,with the degradation efficiency of 31.7%in 240 min.Through the use of radical quenching and surface inhibition experiments,it could be concluded that the interaction between 4-CP and CuMgFe-LDO,rather than free radicals,played a key role in the decomposition of 4-CP,while only the free radicals participated in the MCB degradation process.According to electron paramagnetic resonance and Xray photoelectron spectroscopy data,the formation of a Cu(II)-complex between phenolic hydroxyl groups and surface Cu(II)was primarily responsible for the degradation of phenolic compounds,in which PS accepted one electron from the complex and generated sulfate radicals and chelated radical cations.The chelated radical cations transferred one electron to Cu(Ⅱ)followed by Cu(I)generation and pollutant degradation successively.

STUDIES OF THE INITIATION MECHANISM OF VINYL POLYMERIZATION WITH THE SYSTEM PERSULFATE/N-ALKYL SUBSTITUTED ETHYLENEDIAMINE DERIVATIVES

Effects of N-alkyi substituted ethylenediamine derivatives on vinyl polymerization using persulfate as initiator were studied. The apparent kinetic equations and overall activation energies of acrylamide polymerization were determined using the above mentioned system as initiator. The promoting activities of different diamine derivatives on vinyl polymerization are in the order of tertiary diamine>secondary diamine>primary diamine. Diamines having methyl groups as the substituent on their nitrogen atom possess higher promoting activity than that of having larger alkyl groups. The initial free radicals produced through the redox reaction of persuifate and diamines were studied by spin strapping technique and ESR spectroscopy. The results obtained confirm the fact that the initial free radicals of the diamine species can initiate vinyl polymerization and become the amino end group of the resulting polymers.

Oxidation of ciprofloxacin by the synergistic effect of DBD plasma and persulfate:reactive species and influencing factors analysis

A synergistic system of water falling film dielectric barrier discharge(DBD)plasma and persulfate(PS)was set up and used for oxidizing ciprofloxacin(CIP)in water.Results of reactive species formation in the DBD-only system as well as the DBD–PS system verified the PS activation in the DBD system.Influencing factors on CIP degradation and the degradation process were also been studied.The obtained results showed that the presence of PS could greatly improve the degradation and mineralization of CIP and that the degradation efficiency could reach 97.73%after only 40 min treatment with 4 m M PS addition.The increase of PS concentration,the lower CIP concentration,the acidic solution p H and the addition of metal ions(Fe^(2+)and Cu^(2+))enhanced the CIP degradation,while the existence of Cl^(-)and HCO_(3)^(-)had a negative effect.The experiments related to scavenger addition confirmed the contribution of the main reactive species to the CIP oxidation.Three probable degradation pathways were proposed by analyzing the inorganic ions and organic byproducts formed during the CIP degradation.The toxicity evaluation results of the CIP and its intermediates confirmed the effectiveness of the DBD–PS synergistic system.

A comparison between high temperature catalytic and persulfate oxidation for the determination of total dissolved nitrogen in natural waters

Total dissolved nitrogen(TDN) is an important parameter for assessing the nutrient cycling and status of natural waters.The accurate determination of TDN in natural waters is essential for assessing its contents and distinguishing different forms of nitrogen in the water.The TDN in various systems has been largely documented,and the concentrations of TDN are usually obtained using high-temperature catalytic(HTC) or persulfate oxidation(PO).However,the accuracy of these methods and their suitability for all types of natural waters are still unclear.To explore both methods in-depth,assorted samples were tested,including eight solutions composed of nitrogen-containing compounds(3 dissolved inorganic nitrogen fractions:NO_(3)^(-),NO_(2)^(-)and NH_(4)^(+);5 organic compounds:EDTA-2Na,vitamin B1,vitamin B12,amino acids,and urea) and 105 natural waters which were collected from an open ocean(Northwest Pacific Ocean,28),a marginal sea(Yellow Sea,34),an estuary(Huanghe River mouth,31),rivers(Huanghe River,4;Licun River,4),and precipitations(4 samples).The results showed that heterocycles and molecular dimensions had certain effects on the oxidation efficiency of the PO method but had little effect on HTC.There was no significant difference between the two methods for natural waters,but HTC was more suitable for deep-sea samples with low TDN concentrations(less than 10 μmol/L) and low organic activity.Overall,HTC has a relatively simple measurement process,a high degree of automation,and low error.Therefore,HTC can be recommended to determine the TDN of samples in freshwater and seawater.

Hydrodynamic Cavitation Enhanced SR-Aops Degradation of Organic Pollutants in Water:A Review

SR-AOP(sulfate radical advanced oxidation process)is a novel water treatment method able to eliminate refractory organic pollutants.Hydrodynamic cavitation(HC)is a novel green technology,that can effectively produce strong oxidizing sulfate radicals.This paper presents a comprehensive review of the research advancements in these fields and a critical discussion of the principal factors influencing HC-enhanced SR-AOP and the mechanisms of synergistic degradation.Furthermore,some insights into the industrial application of HC/PS are also provided.Current research shows that this technology is feasible at the laboratory stage,but its application on larger scales requires further understanding and exploration.In this review,some attention is also paid to the design of the hydrodynamic cavitation reactor and the related operating parameters.

A novel advanced oxidation process to degrade organic pollutants in wastewater:Microwave-activated persulfate oxidation

This article, for the first time, provides a novel advanced oxidation process based on sulfate radical （SO^4·-） to degrade organic pollutants in wastewater： microwave （MW）-activated persulfate oxidation （APO） with or without active carbon （AC）. Azo dye acid Orange 7 （AO7） is used as a model compound to investigate the high reactivity of MW-APO. It is found that AO7 （up to 1000 mg/L） is completely decolorized within 5-7 min under an 800 W MW furnace assisted-APO. In the presence of chloride ion （up to 0.50 mol/L）, the decolorization is still 100% completed, though delayed for about 1-2 min. Experiments are made to examine the enhancement by AC. It is exciting to find that the 100% decolorization of AO7 （500 mg/L） is achieved within 3 min by MW-APO using 1.0 g/L AC as catalyst, while the degradation efficiency maintains at 50% by MW energy without persulfate after about 5 min. Besides the destruction of visible light chromophore band of AO7 （484 nm）, during MW-APO, two bands in the ultraviolet region （228 nm and 310 nm） are rapidly broken down. The removal of COD is about 83%-95% for 500 mg/L AO7. SO^4·- is identified with quenching studies using specific alcohols. Both SO^4·- and ·OH could degrade AO7, but SO^4·- plays the dominant role. In a word, MW-APO AC is a new catalytic combustion technology for destruction of organic contamination even for high concentration.

In situ chemical oxidation of aniline by persulfate with iron(Ⅱ) activation at ambient temperature

The kinetics of aniline degradation by persulfate processes with iron（Ⅱ） activation at ambient temperature was investigated in this study.With iron（Ⅱ） as initiator,the oxidation reactions were found to follow a biphasic rate phenomenon：a rapid transformation followed by a slow but sustained oxidation process.In the first 30 s,the reaction mainly relies on the persulfate-Fe^（2＋） reaction in which aniline is oxidized rapidly.After 30 s,the aniline was still oxidized but the rate of reaction tended to be slower and the rates were clearly linear-proportional.After the initial fast oxidation,the reactions appeared to follow a pseudo-first-order model.

Heterogeneous activation of persulfate by CuMgAl layered double oxide for catalytic degradation of sulfameter

In this study,a series of CuMgAl layered double oxides(CuMgAl-LDOs)were obtained via calcination of CuMgAl layered double hydroxides(CuMgAl-LDHs)synthesised via a co-precipitation method.The results show that CuMgAl-LDO can be prepared using an optimal Cu:Mg:Al molar ratio of 3:3:2,NaOH:Na_(2)CO_(3)molar ratio of 2:1,and calcination temperature of 600°C.CuMgAl-LDO is a characteristic of mesoporous material with a lamellar structure and large specific surface area.The removal efficiency of sulfameter(SMD)based on CuMgAl-LDO/persulfate(PS)can reach>98%over a wide range of initial SMD concentrations(5–20 mg L^(-1)).The best removal efficiency of99.49%was achieved within 120 min using 10 mg L^(-1)SMD,0.3 g L^(-1)CuMgAl-LDO,and 0.7 mmol L^(-1)PS.Kinetic analysis showed that the degradation of SMD was in accordance with a quasi-first-order kinetic model.The stability of the CuMgAl-LDO catalyst was verified by the high SMD removal efficiency(>97%within 120 min)observed after five recycling tests and low copper ion leaching concentration(0.89 mg L^(-1)),which is below drinking water quality standard of 1.3 mg L^(-1)permittable in the U.S.Radical scavenging experiments suggest that SO_(4)^(-)is the primary active species participating in the CuMgAl-LDO/PS system.Moreover,our mechanistic investigations based on the radical scavenging tests and X-ray photoelectron spectroscopy(XPS)results indicate that Cu^((II))-Cu^((III))-Cu^((II))circulation is responsible for activating PS in the degradation of SMD and the degradation pathway for SMD was deduced.Accordingly,the results presented in this work demonstrate that CuMgAl-LDO may be an efficient and stable catalyst for the activation of PS during the degradation of organic pollutants.

Activated persulfate by DBD plasma and activated carbon for the degradation of acid orange Ⅱ

In this study, the effect of activated peroxydisulfate(PDS) by dielectric barrier discharge(DBD) plasma and activated carbon(HGAC) on the removal of acid orange Ⅱ(AOⅡ) was investigated. The effects of applied voltage, PDS dosage, HGAC dosage, initial pH value, and inorganic anions on the removal rate of AOⅡ were discussed. The main free radicals degrading azo dyes during the experiment were also studied. Experimental results show that the removal rate of AOⅡ in DBD/HGAC/PDS synergistic system is much higher than that in the single system. With the applied voltage of 16 kV, HGAC dosage of 1 g l-1, PDS and AOⅡ molar ratio of 200:1, initial pH value of 5.4 and concentration of AOⅡ solution of 20 mg l-1, the removal rate of AOⅡ reached 97.6% in DBD/HGAC/PDS process after 28 min of reaction.Acidic and neutral conditions are beneficial for AOⅡ removal. Sulfate and hydroxyl radicals play an important role in the removal of AOⅡ. Inorganic anions are not conducive to the removal of AOⅡ.

Surfactant-assisted removal of 2,4-dichlorophenol from soil by zero-valent Fe/Cu activated persulfate

The organic compounds contaminated soil substantially threatens the growth of plants and food safety.In this study,we synthesis zero-valent bimetallic Fe/Cu catalysts for the degradation of 2,4-dichlorophenol(DCP)in soils with persulfate(PS)in combination of organic surfactants and exploring the main environmental impact factors.The kinetic experiments show that the 5%(mass)dosage of Fe/Cu exhibits a higher degradation efficiency(86%)of DCP in soils,and the degradation efficiency of DCP increases with the increase of the initial PS concentration.Acidic conditions are favorable for the DCP degradation in soils.More importantly,the addition of Tween-80,and Triton-100 can obviously desorb DCP from the soil surface,which enhances the degradation efficiency of DCP in soils by Fe/Cu and PS reaction system.Furthermore,the Quenching experiments demonstrate that SO_(4)^(-1)·and·OH are the predominant radicals for the degradation of DCP during the Fe/Cu and PS reaction system as well as non-radical also exist.The findings of this work provide an effective method for remediating DCP from soils.

Comparison of 1,2,3-Trichloropropane reduction and oxidation by nanoscale zero-valent iron, zinc and activated persulfate

Trichloropropane（TCP） is a chlorinated solvent which derives from chemical manufacturing as a precursor, and it is also an important constituent of solvent formulations in cleaning/degreasing operations. The control and remediation of TCP in polluted sites is a challenge for many conventional remediation techniques due to its refractory behaviour. This challenge in mind, some nano-materials and oxidants were tested to evaluate their effectiveness as in TCP degradation in a laboratory setting. Experimental results indicate that the use of nanoscale zero-valent iron prepared by green tea（GT） as a reductant has negligible degradation effect on TCP under normal temperature and pressure conditions. However, zinc powders of similar size but higher surface reactivity, demonstrated stronger dechlorination capacity in the breakdown of TCP, as almost all of TCP was degraded by carboxymethocel（CMC） stabilized nanoscale zinc within 24 h. Activated persulfate by citric acid（CA） and chelated Fe（Ⅱ） was also used for TCP treatment with a TCP removal efficiency rate of nearly 50% within a 24 h reaction period, and a molar ratio of S2O82-, Fe2+ and CA is 20:5:1. Both the reduction and oxidation reactions are in accordance with the pseudo-first order kinetic equation. These results are promising for future use of TCP for the remediation of polluted sites.

Application of persulfate in low-temperature atmospheric-pressure plasma jet for enhanced treatment of onychomycosis

Fungal infection of human nails,or onychomycosis,affects 10%of the world's adult population,but current therapies have various drawbacks.In this work,we employed a self-made low-temperature plasma(LTP)device,namely,an atmospheric-pressure plasma jet(APPJ)device to treat the nails infected with Trichophyton rubrum(T.rubrum)with the aid of persulfate solution.We found that persulfate solution had a promoting effect on plasma treatment of onychomycosis.With addition of sodium persulfate,the APPJ therapy could cure onychomycosis after several times of treatment.As such,this work has demonstrated a novel and effective approach which makes good use of LTP technique in the treatment of onychomycosis.

A New Rechargeable Battery Design Based on Magnesium and Persulfate

A battery concept based on the chemical system of magnesium (anode) and persulfate (cathode) is presented. A complete procedure is given to prepare the battery for testing, although no experimental data is presented herein. The similarities of this system to a well-tested Li||LiFePO4 system lend strong credibility to the concept, and the estimated performance characteristics presented. The advantages of this design include the following many areas. First, inexpensive, and available, battery reagents exist. Second, by analogy to the lithium ion battery for which comparisons are made, the full fabrication process for battery separator design is known and efficient;and both the kJ/kg and Amps/kg values are estimated to be substantially larger than the lithium ion battery (e.g., Li||LiFePO4) experimental design. Finally, flammability of the Mg||MgS2O8 system can be expected to provide less of a potential flammability concern, compared to comparable lithium ion batteries. This is because lithium metal, as with any alkali metal, is aggressively flammable even under reduced moisture environments. The proposed magnesium persulfate battery calculated metrics yield an improvement of 194% greater output power (W/cm2&middotkg), and 154% greater stored energy (MJ/kg) than state-of-the-art lithium iron phosphate batteries.