Ascorbic acid enhanced the circulation between Fe(II) and Fe(III) in peroxymonosulfate system for fluoranthene degradation.

In this research, ascorbic acid (AA) was used to enhance Fe(II)/Fe(III)-activated permonosulfate (PMS) systems for the degradation of fluoranthene (FLT). AA enhanced the production of ROS in both PMS/Fe(II) and PMS/Fe(III) systems through chelation and reduction and thus improved the degradation performance of FLT. The optimal molar ratio in PMS/Fe(II)/AA/FLT and PMS/Fe(III)/AA/FLT processes were 2/2/4/1 and 5/10/5/1, respectively. In addition, the experimental results on the effect of FLT degradation under different groundwater matrixes indicated that PMS/Fe(III)/AA system was more adaptable to different water quality conditions than the PMS/Fe(II)/AA system. SO4·- was the major reactive oxygen species (ROS) responsible for FLT removal through the probe and scavenging tests in both systems. Furthermore, the degradation intermediates of FLT were analyzed using gas chromatograph-mass spectrometry (GC-MS), and the probable degradation pathways of FLT degradation were proposed. In addition, the removal of FLT was also tested in actual groundwater and the results showed that by increasing the dose and pre-adjusting the solution pH, 88.8 and 100% of the FLT was removed for PMS/Fe(II)/AA and PMS/Fe(III)/AA systems. The above experimental results demonstrated that PMS/Fe(II)/AA and PMS/Fe(III)/AA processes have a great perspective in practice for the rehabilitation of FLT-polluted groundwater.

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.

Enhanced multi-metals stabilization: Synergistic insights from hydroxyapatite and peroxide dosing strategies.

Sediment contamination by heavy metals is a pressing environmental concern. While in situ metal stabilization techniques have shown promise, a great challenge remains in the simultaneous immobilization of multi-metals co-existing in contaminated sediments. This study aims to address this challenge by developing a practical method for stabilizing multi-metals by hydroxyapatite and calcium peroxide (HAP/CaO2) dosing strategies. Results showed that dosing 15.12 g of HAP/CaO2 at a ratio of 3:1 effectively transformed labile metals into stable fractions, reaching reaction kinetic equilibrium within one month with a pseudo-second-order kinetic (R2 > 0.98). The stable fractions of Nickel (Ni), Chromium (Cr), and lead (Pb) increased by approximately 16.9 %, 26.7 %, and 21.9 %, respectively, reducing heavy metal mobility and ensuring leachable concentrations complied with the stringent environmental Class I standard. Mechanistic analysis indicated that HAP played a crucial role in Pb stabilization, exhibiting a high rate of 0.0176 d-1, while Cr and Ni stabilization primarily occurred through the formation of hydroxide precipitates, as well as the slowly elevated pH (>8.5). Importantly, the proposed strategy poses a minimal environmental risk to benthic organisms exhibits almost negligible toxicity towards Vibrio fischeri and the Chironomus riparius, and saves about 71 % of costs compared to kaolinite. These advantages suggest the feasibility of HAP/CaO2 dosing strategies in multi-metal stabilization in contaminated sediments.

Cyanide-Isolated Cobalt Catalyst for Ultraefficient Advanced Oxidation Treatment.

Catalyst design with a "Co-N-C" structure at the atomic level has shown great interest for peroxymonosulfate (PMS) activation toward advanced oxidation water treatment. Here, we present an innovative way of producing cobalt hexacyanocobaltate (Co-HCC) with an abundance of atomically isolated CoII-NC sites at the outer surface. This material allows ultraefficient PMS activation to generate plenty of sulfate and hydroxyl radicals, with a turnover frequency much higher than those of most cobalt-based catalysts reported so far and even the homogeneous catalysis by Co2+ ions. We gained fundamental insights on its unprecedently high catalytic performance based on experimental results and computational study. Then, we controlled the growth of Co-HCC on a ceramic membrane to form a confined oxidation environment that utilizes the extended surface area and maximal exposure of short-lived radicals for a fast removal of organic pollutants that enter the pores. As a result, this catalytic membrane achieves complete disruption of micropollutants under a water flux up to 10,000 LMH (merely 0.2 s retention time) and further >90% mineralization of organic pollutants in complex industrial wastewater matrices (<100 s retention time), together with the merits of operational simplicity and great longevity (2 weeks continuous run). Our study elicits a new milestone in "Co-N-C" catalyst structure design for PMS activation and highlights the great interest of producing catalytic membranes for a confined treatment of organic pollutants from partial oxidation to complete mineralization as a new benchmark.

MnFe layered double hydroxides confined MnOx for peroxymonosulfate activation: A novel manner for the selective production of singlet oxygen.

Singlet oxygen (1O2) is a reactive species for the selective degradation of stubborn organic pollutants. Given its resistance to harsh water environment, the effective and exclusive generation of 1O2 is acknowledged as a key strategy to mitigate water production costs and ensure water supply safety. Herein, we synthesized MnOx intercalated MnFe layered double hydroxides (MF-MnOx) to selectively produce 1O2 through the activation of PMS. The distinctive confined structure endowed MF-MnOx with a special pathway for the PMS activation. The direct oxidation of BPA on the intercalated MnOx induced the charge imbalance in the MnFe-LDH layer, resulting in the selective generation of 1O2. Moreover, acceptable activity deterioration of MF-MnOx was observed in a 10 h continuous degradation test in actual water, substantiating the application potential of MF-MnOx. This work presents a novel catalyst for the selective production of 1O2, and evaluates its prospects in the remediation of micro-polluted water.

Synergistic oxidation induced by underwater bubbling plasma and diatomite-CoFe2O4 activated peroxymonosulfate for the degradation of ciprofloxacin hydrochloride.

Underwater bubbling plasma (UBP) coupled with diatomite-CoFe2O4 (Dt-CFO) activated peroxymonosulfate (PMS) was proposed for the degradation of ciprofloxacin hydrochloride (CIP) in this work. The catalyst sample of Dt-CFO with large specific surface area, rich active sites and excellent magnetic property was prepared by the hydrothermal method and systematically characterized to investigate its material properties. The combination of UBP and Dt-CFO activated PMS (UBP/Dt-CFO/PMS) showed excellent synergy with the synergistic factor of 1.98, and reached the CIP degradation percentage of 94.7%, which corresponded to the kinetic constant of 0.097 min-1. Dt-CFO with the diatomite content of 30 wt% achieved the best catalytic activity in the reaction system. Higher catalyst and PMS dose, peak voltage, pulse frequency and lower initial CIP concentration were beneficial for CIP removal. The addition of Cl-, HCO3-, SO42- and humic acid suppressed CIP degradation, while NO3- had no effect on CIP removal. The Dt-CFO composite exhibited excellent reusability and low leaching metal amount, demonstrating its good stability. SO4-·, ·OH, ·O2-, 1O2, eaq, O3 and H2O2 were the active species confirmed to be involved in CIP degradation. The redox circles of ≡ Co(Ⅱ)/≡Co(Ⅲ) and ≡ Fe(Ⅱ)/≡Fe(Ⅲ) on Dt-CFO surface and the plasma-induced physicochemical effects dominated PMS activation. The decomposition process of CIP was explored through fluorescence spectra. Three degradation pathways were inferred, and the toxicity analysis showed the toxicity of CIP solution weakened after discharge treatment.

Nitrogen-doped metal-free granular activated carbons as economical and easily separable catalysts for peroxymonosulfate and hydrogen peroxide activation to degrade bisphenol A.

The fabrication of low-cost, highly efficient, environmentally friendly, and easily separable metal-free heterogeneous catalysts for environmental remediation remains a challenge. In this study, granular nitrogen-doped highly developed porous carbons with a particle size of 0.25-0.30 mm were prepared by preoxidation and subsequent NH3 modification of a commercially available coconut-based activated carbon, and used to activate peroxymonosulphate (KHSO5) or hydrogen peroxide (H2O2) to degrade bisphenol A (BPA). The nitrogen-doped carbon (ACON-950) prepared by NH3 modification at 950 °C, with the addition of only 0.15 g/L could remove 100% of 50 mg/L BPA in 150 min, and more than 90% of the removed BPA was due to degradation. The removal rates of total organic carbon of ACON-950/KHSO5 and ACON-950/H2O2 systems reached 60.4% and 66.2% respectively, indicating the excellent catalytic activity of ACON-950. The reaction rate constant was significantly positively correlated with the absolute content of pyridinic N (N-6) and graphitic N (N-Q) and negatively and weakly positively correlated with pyrrolic N (N-5) and defects. Quenching experiments combined with electron paramagnetic resonance demonstrated that singlet oxygen was the dominant reactive oxidative species for BPA degradation. ACON-950 was characterized before and after the degradation reaction using N2 adsorption-desorption analyzer, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The results confirmed the prominent contribution of both the N-6 and N-Q to the catalytic performance of nitrogen-doped carbons. The reusability of ACON-950 and its application in actual water bodies further demonstrated its remarkable potential for the remediation of organic pollutants in wastewater.

Why is HSO5- so effective against bacteria? Insights into the mechanisms of Escherichia coli disinfection by unactivated peroxymonosulfate.

This study examined the antimicrobial efficacy of peroxymonosulfate (PMS) against bacteria, using Escherichia coli (E. coli) as a model organism. Our investigation delineates the complex mechanisms exerted by unactivated PMS. Thus, an initial redox reaction between PMS and the target biomolecules of bacteria generates SO4•- as the pivotal reactive species for bacterial inactivation; to a lesser extent, •OH, 1O2, or O2•- may also participate. Damage generated during oxidation was identified using an array of biochemical techniques. Specifically, redox processes are promoted by PMS and SO4•- targets and disrupt various components of bacterial cells, predominantly causing extracellular damage as well as intracellular lesions. Among these, external events are the key to cell death. Finally, by employing gene knockout mutants, we uncovered the role of specific gene responses in the intracellular damage induced by radical pathways. The findings of this study not only expand the understanding of PMS-mediated bacterial inactivation but also explain the ten-fold higher effectiveness of PMS than that reported for H2O2. Hence, we provide clear evidence that unactivated PMS solutions generate SO4•- in the presence of bacteria, and consequently, should be considered an effective disinfection method.

The correlation between electron exchange capacity of Fenton-like heterogeneous catalyst and catalytic activity.

Electron transfer played key role in peroxymonosulfate (PMS) activation for heterogeneous Fenton-like catalysts (HFCs). However, the relationship between electron exchange capacity (EEC) and catalytic activity of HFCs has not been elucidated. Herein, thirteen HFCs reported in our previous studies were selected to measure their EEC via electrochemical methods and to investigate the correlation between EEC and catalytic activity for PMS. The results show that nitrogen-doped graphene oxide had much higher EEC (5.299 mM(e) g-1), followed by reduced graphene oxide (3.23 mM(e) g-1), nitrogen-doped biochar-700 (2.032 mM(e) g-1), graphene oxdie (1.789 mM(e) g-1), nitrogen-doped biochar-300 (1.15 mM(e) g-1), g-C3N4 (0.752 mM(e) g-1) and biochar (0.351 mM(e) g-1). For carbon materials, their catalytic activity was not determined by electron donor capacity (EDC), electron acceptor capacity (EAC) and EEC (EDC + EAC), but was linear correlation with |EDC-EAC| that can characterize the extent of HFCs reacting with PMS. The higher the |EDC-EAC| is, the higher the catalytic activity of HFCs is. For carbonaceous materials, their catalytic activity was not proportional to EAC, but had good linear correlation with EDC and |EDC-EAC|. The discrepancy between carbon materials and carbonaceous materials could be due to the different activation mechanisms. Further analysis found that there was no correlation between EEC and the reactive species derived from PMS, indicating that the produced reactive species was not only controlled by EEC. This study firstly elucidated the correlation between EEC and catalytic activity of HFCs, and |EDC-EAC| could be used as an index for evaluating the catalytic activity of HFCs.

Edge interface microenvironment regulation of CoOOH/commercial activated carbon nano-hybrids enabling PMS activation for degrading ciprofloxacin.

Peroxymonosulfate (PMS) is widely employed to generate oxygen-containing reactive species for ciprofloxacin (CIP) degradation. Herein, cobalt oxyhydroxide @activated carbon (CoOOH@AC) was synthesized via a wet chemical sedimentation method to activate PMS for degradation of CIP. The result suggested AC can support the vertical growth of CoOOH nanosheets to expose high-activity Co-contained edges, possessing efficient PMS activation and degradation activity and catalytic stability. In the presence of 3.0 mg of optimal CoOOH@AC and 2 mM PMS, 96.8 % of CIP was degraded within 10 min, approximately 11.6 and 9.97 times greater than those of CoOOH/PMS and AC/PMS systems. Notably, it was disclosed that the optimal CoOOH@AC/PMS system still exhibited efficient catalytic performance in a wide pH range, different organics and common co-existing ions. Quenching experiments and electron paramagnetic resonance indicated that both radical and non-radical processes contributed to the degradation of CIP, with 1O2 and direct electron transfer accounting for the non-radical pathway and SO4•- and •OH serving as the main radical active species. Finally, possible CIP degradation pathways were proposed based on high-performance liquid chromatography-mass spectrometry. This study provided an alternate method for wastewater treatment based on PMS catalyzed by cobalt-based hydroxide.

A novel remediation strategy of mixed calcium peroxide and degrading bacteria for polycyclic aromatic hydrocarbon contaminated water.

Polycyclic aromatic hydrocarbons (PAHs) are a class of toxic organic pollutants commonly detected in the aqueous phase. Traditional biodegradation is inefficient and advanced oxidation technologies are expensive. In the current study, a novel strategy was developed using calcium peroxide (CP) and PAH-degrading bacteria (PDB) to effectively augment PAH degradation by 28.62-59.22%. The PDB consisted of the genera Acinetobacter, Stenotrophomonas, and Comamonas. Applying the response surface model (RSM), the most appropriate parameters were identified, and the predictive degradation rates of phenanthrene (Phe), pyrene (Pyr), and ΣPAHs were 98%, 76%, and 84%, respectively. The constructed mixed system could reduce 90% of Phe and more than 60% of ΣPAHs and will perform better at pH 5-7 and lower salinity. Because PAHs tend to bind to dissolved organic matter (DOM) with larger molecular weights, humic acid (HA) had a larger negative effect on the PAH-degradation efficiency of the CP-PDB mixed system than fulvic acid (FA). The proposed PAH-degradation pathways in the mixed system were based on the detection of intermediates at different times. The investigation constructed and optimized a novel environmental PAH-degradation strategy. The synergistic application of PDB and oxidation was extended for organic contaminant degradation in aqueous environments.

Hollow CoP/carbon as an efficient catalyst for the peroxymonosulfate activation derived from phytic acid assisted metal-organic framework.

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

2D/2D heterojunctions for rapid and self-cleaning removal of antibiotics via visible light-assisted peroxymonosulfate activation: Efficiency, synergistic effects, and applications.

Developing eco-friendly and efficient technologies for treating antibiotic wastewater is crucial. Traditional methods face challenges in incomplete removal, high costs, and secondary pollution. Heterogeneous peroxymonosulfate (PMS) activation assisted by visible light shows promise, but suitable activators remain a huge challenge. Here, we synthesized cost-effective carbon nitride/bismuth bromide oxide (CN/BiOBr) heterojunctions. Such a heterojunction achieved rapid PMS activation, achieving over 90.00% tetracycline (TC) removal only within 1 min (kobs of 2.23 min-1), surpassing previous systems by nearly 1-2 orders of magnitude and even remarkably superior to the popular single-atom catalysts. The system exhibited self-cleaning properties, maintaining activity after 8 cycles and stability across a wide pH range (3.01 to 9.03). Quenching experiments and theoretical calculations elucidated the exclusive •O2- species involvement and removal pathways. Eco-toxicity assessment and total organic carbon results confirmed simultaneous degradation, detoxification, and mineralization. This system also showed excellent resistance to environmental factors, e.g., coexisting anions, varying pH, and water sources, and demonstrated potential in coking and medical wastewater purification. This study presents a novel technique for rapidly decontaminating antibiotic wastewater through visible light-assisted PMS activation and introduces innovative bionic catalytic oxidation combining light and darkness for practical applications.

Degradation of 2, 4-dichlorophenol by peroxymonosulfate catalyzed by ZnO/ZnMn2 O4.

In this study, a highly efficient peroxymonosulfate (PMS) activator, ZnO/ZnMn2 O4 , was synthesized using a simple one-step hydrothermal method. The resulting bimetallic oxide catalyst demonstrated a homogenous and high-purity composition, showcasing synergistic catalytic activity in activating PMS for degrading 2, 4-dichlorophenol (2, 4-DCP) in aqueous solution. This catalytic performance surpassed that of individual ZnO, Mn2 O3 , and ZnMn2 O4 metal materials. Under the optimized conditions, the removal efficiency of 2, 4-DCP reached approximately 86% within 60 min, and the catalytic ability remained almost constant even after four cycles of recycling. The developed degradation system proved effective in degrading other azo-dye pollutants. Certain inorganic anions such as HPO4 - , HCO3 - , and NO3 - significantly inhibited the degradation of 2, 4-DCP, while Cl- and SO4 2- did not exhibit such interference. Results from electrochemical experiments indicated that the electron transfer ability of ZnO/ZnMn2 O4 surpassed that of individual metals, and electron transfer occurred between ZnO/ZnMn2 O4 and the oxidant. The primary active radicals responsible for degrading 2, 4-DCP were identified as SO4 •- , OH• and O2 •- , generated through the oxidation and reduction of PMS catalyzed by Zn (II) and Mn (III). Furthermore, X-ray photoelectron spectroscopy (XPS) analysis of the fresh and used catalysts revealed that the exceptional electron transfer ability of ZnO facilitated the valence transfer of Mn (III) and the transfer of electrons to the catalyst's oxygen surface, thus enhancing the catalytic efficiency. The analysis of radicals and intermediates indicates that the two main pathways for degrading 2, 4-DCP involve hydroxylation and radical attack on its aromatic ring. PRACTITIONER POINTS: A bimetallic ZnO/ZnMn2 O4 catalyst was synthesized and characterized. ZnO/ZnMn2 O4 can synergistically activate PMS to degrade 2, 4-DCP compared with single metal oxide. Three primary active radicals, O2 •- , • OH, and SO4 •- , were generated to promote the degradation. ZnO promoted electron transfer among the three species of Mn to facilitate oxidizing pollutants. Hydroxylation and radical attack on the aromatic ring of 2, 4-DCP are the two degradation pathways.

Influence mechanism of anions on iron doping into swine bone char: Promoting non-radical oxidation of acetaminophen in a Fenton-like system.

The application of iron-doped biochar in peroxymonosulfate (PMS) activation systems has gained increasing attention due to their effectiveness and environmental friendliness in addressing environmental issues. However, the behavioral mechanism of iron doping and the detailed 1O2 generation mechanism in PMS activation systems remain ambiguous. Here, we investigated the effects of three anions (Cl-, NO3-and SO42-) on the process of iron doping into bone char, leading to the synthesis of three iron-doped bone char (Fe-ClBC, Fe-NBC and Fe -SBC). These iron-doped bone char were used to catalyze PMS to degrade acetaminophen (APAP) and exhibited the following activity order: Fe-ClBC > Fe-NBC > Fe-SBC. Characterization results indicated that iron doping primarily occurred through the substitution of calcium in hydroxyapatite within BC. In the course of the impregnation, the binding of SO42- and Ca2+ hindered the exchange of iron ions, resulting in lower catalytic activity of Fe-SBC. The primary reactive oxygen species in the Fe-ClBC/PMS and Fe-NBC/PMS systems were both 1O2. 1O2 is produced through O2•- conversion and PMS self-dissociation, which involves the generation of metastable iron intermediates and electron transfer within iron species. The presence of oxygen vacancies and more carbon defects in the Fe-ClBC catalyst facilitates 1O2 generation, thereby enhancing APAP degradation within the Fe-ClBC/PMS system. This study is dedicated to in-depth exploration of the mechanisms underlying iron doping and defect materials in promoting 1O2 generation.

Bromide triggers efficient peroxymonosulfate activation for phosphonate degradation.

Phosphonates have received a widespread attention in wastewater treatment due to their potential threat to the water environment. Advanced oxidation processes (AOPs) are feasible methods to degrade phosphonates, and most of the coexisting substances in water show a negative factor during their oxidation. However, the effect of bromide (Br-) on the degradation of phosphonates in peroxymonosulfate (PMS) activation is still unclear. Herein, using 1-hydroxyethane 1,1-diphosphonic acid (HEDP) as a target phosphonate, Br- could remarkably enhance the degradation of HEDP in PMS activation compared to the PMS alone. Under the condition of pH = 7.0, the optimal degradation efficiency of HEDP is 84.8% in the PMS/Br- process after 30-min reaction, whereas no significant oxidation is obtained in the PMS/I- and PMS/Cl- processes. Multiple experiments (i.e., electron paramagnetic resonance (EPR), radical quenching experiments and chemical probs) confirm that free bromine, SO4•- and HO• paly a minor role in HEDP removal, and bromine radical species make a dominant responsible for HEDP oxidation. Additionally, NO3-, SO42-, Cl-, and HCO3- have a little effect on the degradation of HEDP, but the HEDP removal is greatly inhibited in the presence of humic acid (HA). However, the degradation efficiency of HEDP using PMS/Br- process in river and sewage is a much higher than UV/persulfate (PDS) and UV/H2O2 processes. This study provides a new sight into the effect of Br- on the degradation phosphonates in PMS activation process.

Synthesis and Characterization of Organic Peroxides from Monoterpene-Derived Criegee Intermediates in Secondary Organic Aerosol.

Ozonolysis of alkenes is known to produce reactive intermediates─stabilized Criegee intermediates (SCIs), and their subsequent bimolecular reactions with various carboxylic acids can form α-acyloxyalkyl hydroperoxides (AAHPs), which is considered a major class of organic peroxides in secondary organic aerosol (SOA). Despite their atmospheric and health importance, the molecular-level identification of organic peroxides in atmospheric aerosols is highly challenging, preventing further assessment of their environmental fate. Here, we synthesize 20 atmospherically relevant AAHPs through liquid-phase ozonolysis, in which two types of monoterpene-derived SCIs from either α-pinene or 3-carene are scavenged by 10 different carboxylic acids to form AAHPs with diverse structures. These AAHPs are identified individually by liquid chromatography coupled with high-resolution mass spectrometry. AAHPs were previously thought to decompose quickly in an aqueous environment such as cloud droplets, but we demonstrate here that AAHPs hydrolysis rates are highly compound-dependent with rate constants differing by 2 orders of magnitude. In contrast, the aqueous-phase formation rate constants between SCI and various carboxylic acids vary only within a factor of 2-3. Finally, we identified two of the 20 synthesized AAHPs in α-pinene SOA and two in 3-carene SOA, contributing ∼0.3% to the total SOA mass. Our results improve the current molecular-level understanding of organic peroxides and are useful for a more accurate assessment of their environmental fate and health impact.

Surface reconstructed Fe@C1000 for enhanced Fenton-like catalysis: Sustainable ciprofloxacin degradation and toxicity reduction.

The Fe-based catalysts typically undergo severe problems such as deactivation and Fe sludge emission during the peroxymonosulfate (PMS) activation, which commonly leads to poor operation and secondary pollution. Herein, an S-doped Fe-based catalyst with a core-shell structure (Fe@CT, T = 1000°C) was synthesized, which can solve the above issues via the dynamic surface evolution during the reaction process. Specifically, the Fe0 on the surface of Fe@C1000 could be consumed rapidly, leaving numerous pores; the Fe3C from the core would subsequently migrate to the surface of Fe@C1000, replenishing the consumed active Fe species. The X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses demonstrated that the reaction surface reconstructed during the PMS activation, which involved the FeIII in-situ reduction by S species as well as the depletion/replenishment of effective Fe species. The reconstructed Fe@C1000 achieved near-zero Fe sludge emission (from 0.59 to 0.08-0.23 mg L-1) during 5 cycles and enabled the dynamic evolution of dominant reactive oxygen species (ROS) from SO4·- to FeIVO, sustainably improving the oxidation capacity (80.0-92.5% in following four cycles) to ciprofloxacin (CIP) and reducing the toxicity of its intermediates. Additionally, the reconstructed Fe@C1000/PMS system exhibited robust resistance to complex water matrix. This study provides a theoretical guideline for exploring surface reconstruction on catalytic activity and broadens the application of Fe-based catalysts in the contaminants elimination.

Ce/N @BC prepared based on plant metallurgy strategy: A novel activator of peroxymonosulfate for the degradation of sulfamethoxazole.

A novel carbon catalyst was created based on plant metallurgy strategy for organic pollutants removal. Plants rich in CeO2 NPs in water were used as carbon precursors and pyrolyzed with urea to obtain Ce/N co-doped carbon catalysts, which were used in the degradation of sulfamethoxazole (SMX) by active peroxymonosulfate (PMS). The results showed that the Ce/N @BC/PMS system achieved to 94.5% degradation of SMX in 40 min at a rate constant of 0.0602 cm-1. The activation center of PMS is widely dispersed Ce oxide nanocrystals, and CeO2 NPs promote the formation of oxygen centered PFR with enhanced catalytic ability and longer half-life. In addition, N-doping facilitates the transfer of π-electrons within the sp2 carbon of biochar, increasing active sites and thus improving PMS activation efficiency. The degradation process was contributed to by both radical and non-radical activation mechanisms including 1O2 and direct electron transfer, with O2•- serving as 1O2's precursor. Through the DFT calculations, LC-MS and toxicological analyses, the degradation pathway of pollutants and the toxicity changes throughout the entire degradation process were further revealed, indicating that the degradation of SMX could effectively reduce ecological toxicity.

Confined Co@NCNTs as highly efficient catalysts for activating peroxymonosulfate: free radical and non-radical co-catalytic mechanisms.

A series of transition metal (Co, Ni, Fe) nanoparticles were confined in N-doped carbon nanotubes (NCNTs) prepared (Co@NCNTs, Ni@NCNTs, and Fe@NCNTs) by the polymerization method. The structure and composition of catalysts were well characterized. The catalytic activity of catalysts for activating peroxymonosulfate (PMS) was conducted via acid orange 7 (AO7) degradation. Among the catalysts, Co@NCNTs performed the best catalytic activity. Additionally, Co@NCNTs performed good catalytic activity in pH values of 2.39-10.98. Cl- and SO42- played a promoting roles in AO7 degradation. NO3- presented a weak effect on the catalytic performance of Co@NCNTs, while HCO3- and CO32- significantly suppressed the catalytic performance of Co@NCNTs. Both non-radical (1O2 and electron transfer) and free-radical (·OH and SO4·-) pathways were detected in the Co@NCNTs/PMS system. Notably, 1O2 was identified to be the main active specie in this study. The catalytic activity of Co@NCNTs gradually decreased after cycle reuse of Co@NCNTs. Finally, the toxicity of the AO7 degradation solution in the study was evaluated by Chlorella pyrenoidosa.