Microalgae enhanced co-metabolism of sulfamethoxazole using aquacultural feedstuff components: Co-metabolic pathways and enzymatic mechanisms.

The application of antibiotics in freshwater aquaculture leads to increased contamination of aquatic environments. However, limited information is available on the co-metabolic biodegradation of antibiotics by microalgae in aquaculture. Feedstuffs provide multiple organic substrates for microalgae-mediated co-metabolism. Herein, we investigated the co-metabolism of sulfamethoxazole (SMX) by Chlorella pyrenoidosa when adding main components of feedstuff (glucose and lysine). Results showed that lysine had an approximately 1.5-fold stronger enhancement on microalgae-mediated co-metabolism of SMX than glucose, with the highest removal rate (68.77% ± 0.50%) observed in the 9-mM-Lys co-metabolic system. Furthermore, we incorporated reactive sites predicted by density functional theory calculations, 14 co-metabolites identified by mass spectrometry, and the roles of 18 significantly activated enzymes to reveal the catalytic reaction mechanisms underlying the microalgae-mediated co-metabolism of SMX. In lysine- and glucose-treated groups, five similar co-metabolic pathways were proposed, including bond breaking on the nucleophilic sulfur atom, ring cleavage and hydroxylation at multiple free radical reaction sites, together with acylation and glutamyl conjugation on electrophilic nitrogen atoms. Cytochrome P450, serine hydrolase, and peroxidase play crucial roles in catalyzing hydroxylation, bond breaking, and ring cleavage of SMX. These findings provide theoretical support for better utilization of microalgae-driven co-metabolism to reduce sulfonamide antibiotic residues in aquaculture.

Integrated AI-driven optimization of Fenton process for the treatment of antibiotic sulfamethoxazole: Insights into mechanistic approach.

Antibiotics, as a class of environmental pollutants, pose a significant challenge due to their persistent nature and resistance to easy degradation. This study delves into modeling and optimizing conventional Fenton degradation of antibiotic sulfamethoxazole (SMX) and total organic carbon (TOC) under varying levels of H2O2, Fe2+ concentration, pH, and temperature using statistical and artificial intelligence techniques including Multiple Regression Analysis (MRA), Support Vector Regression (SVR) and Artificial Neural Network (ANN). In statistical metrics, the ANN model demonstrated superior predictive accuracy compared to its counterparts, with lowest RMSE values of 0.986 and 1.173 for SMX and TOC removal, respectively. Sensitivity showcased H2O2/Fe2+ ratio, time and pH as pivotal for SMX degradation, while in simultaneous SMX and TOC reduction, fine tuning the time, pH, and temperature was essential. Leveraging a Hybrid Genetic Algorithm-Desirability Optimization approach, the trained ANN model revealed an optimal desirability of 0.941 out of 1000 solutions which yielded a 91.18% SMX degradation and 87.90% TOC removal under following specific conditions: treatment time of 48.5 min, Fe2+: 7.05 mg L-1, H2O2: 128.82 mg L-1, pH: 5.1, initial SMX: 97.6 mg L-1, and a temperature: 29.8 °C. LC/MS analysis reveals multiple intermediates with higher m/z (242, 270 and 288) and lower m/z (98, 108, 156 and 173) values identified, however no aliphatic hydrocarbon was isolated, because of the low mineralization performance of Fenton process. Furthermore, some inorganic fragments like NH4+ and NO3- were also determined in solution. This comprehensive research enriches AI modeling for intricate Fenton-based contaminant degradation, advancing sustainable antibiotic removal strategies.

Migration and transformation behaviors of antibiotics in water-sediment system under simulated light and wind waves.

Antibiotics can generally be detected in the water-sediment systems of lakes. However, research on the migration and transformation of antibiotics in water-sediment systems based on the influences of light and wind waves is minimal. To address this research gap, we investigated the specific impacts of light and wind waves on the migration and transformation of three antibiotics, norfloxacin (NOR), trimethoprim (TMP), and sulfamethoxazole (SMX), under simulated light and wind waves disturbance conditions in a water-sediment system from Taihu Lake, China. In the overlying water, NOR was removed the fastest, followed by TMP and SMX. Compared to the no wind waves groups, the disturbance of big wind waves reduced the proportion of antibiotics in the overlying water. The contributions of light and wind waves to TMP and SMX degradation were greater than those of microbial degradation. However, the non-biological and biological contributions of NOR to degradation were almost equal. Wind waves had a significant impact on the microbial community changes in the sediment, especially in Methylophylaceae. These results verified the influence of light and wind waves on the migration and transformation of antibiotics, and provide assistance for the risk of antibiotic occurrence in water and sediments.

Formation of cation bridges and its promoting mechanism for sorption of sulfamethoxazole by montmorillonite.

The coexistence of metal cations is often accompanied by organic pollution and could affect the environmental fate of organics by mediating the formation of cation bridges. However, the environmental fate and risk of organics in cation co-existing environments are poorly understood due to the lack of accurate identification of cation bridge formation and stability. In this study, the sorption of sulfamethoxazole (SMX) on montmorillonite (MT) with the coexistence of three different valence metal cations (Na+, Ca2+, and Cr3+) was investigated. Ca2+ and Cr3+ can significantly promote the sorption of SMX on MT for about 5∼10 times promotion, respectively, while Na+ bridges displayed little effect on the sorption of SMX. The sorption binding energy of SMX with MT-Ca (-44.01 kcal/mol) and MT-Cr (-64.57 kcal/mol) bridges was significantly lower than that with MT-Na (-38.45 kcal/mol) and MT (-39.39 kcal/mol), indicating that the sorption affinity of SMX on Cr and Ca bridges was much stronger. The higher valence of the cations also resulted in a more stable adsorbed SMX with less desorption fluctuation. In addition, the relatively higher initial concentration of SMX and the valence of cations increased the bonding density of the cation bridges, thus promoting the apparent sorption of SMX on MT to a certain extent. This work reveals the formation and function of cation bridges in the sorption of SMX on MT. It lays a theoretical foundation for further understanding the environmental fate and risk of organics.

Adsorption of sulfamethoxazole and lincomycin from single and binary aqueous systems using acid-modified biochar from activated sludge biomass.

The extensive use of pharmaceuticals has raised growing concerns regarding their presence in surface waters. High concentrations of sulfamethoxazole (SMX) and lincomycin (LIN), as commonly prescribed antibiotics, persist in various wastewaters and surface waters, posing risks to public health and the environment. Biochar derived from accessible biowaste, like activated sludge biomass, offers a sustainable and eco-friendly solution to mitigate antibiotic release into water systems. This study investigates the effectiveness of H3PO4-modified activated sludge-based biochar (PBC) synthesized through microwave (MW) heating for the adsorption of SMX and LIN antibiotics. The synthesis parameters of PBC were optimized using a central composite design considering MW power, time, and H3PO4 concentration. Characterization results validate the efficacy of the synthesis process creating a specific surface area of 365 m2/g, and well-developed porosity with abundant oxygen-containing functional groups. Batch and dynamic adsorption experiments were piloted to assess the adsorption performance of PBC in single and binary antibiotic systems. Results show that PBC exhibits a higher affinity for SMX rather than LIN, with maximum adsorption capacities of 45.6 mg/g and 26.6 mg/g, respectively. Based on kinetic studies chemisorption is suggested as the primary mechanism for SMX and LIN removal. Equilibrium studies show a strong agreement with the Redlich-Peterson isotherm, suggesting a composite adsorption mechanism with a greater probability of multilayer adsorption for both antibiotics. Hydrogen bonding and π-π electron sharing are suggested as the prevailing adsorption mechanisms of SMX and LIN on the modified biochar. Furthermore, a dynamic adsorption system was replicated using a fixed bed column setup, demonstrating effective removal of SMX and LIN from pure water and real wastewater samples using PBC-loaded hydrogel beads (PBC-B). These findings serve as crucial support for upcoming studies concerning the realistic application of sludge-based biochar in the removal of antibiotics from water systems.

Adsorption effects of electron scavengers and inorganic ions on catalysts for catalytic oxidation of sulfamethoxazole in radiation treatment.

This study aimed to investigate adsorption effects of electron scavengers (H2O2 and S2O82-) on oxidation performance for mineralization of sulfamethoxazole (SMX) in radiation treatment using catalysts (Al2O3, TiO2). Hydrogen peroxide (H2O2, 1 mM) as an electron scavenger showed weak adsorption onto catalysts (0.012 mmol g-1-Al2O3 and 0.004 mmol g-1-TiO2, respectively), leading to an increase in TOC removal efficiency of SMX within the absorbed dose of 30 kGy by 12.3% with Al2O3 and by 8.0% with TiO2. The weak adsorption of H2O2 onto the catalyst allowed it to act as an electron scavenger, promoting indirect decomposition reactions. However, high adsorption of S2O82- (1 mM) onto Al2O3 (0.266 mmol g-1-Al2O3) showed a decrease in TOC removal efficiency of SMX from 76.2% to 30.2% within the absorbed dose of 30 kGy. The high adsorption of S2O82- onto the catalyst inhibited direct decomposition reaction by reducing adsorption of SMX on catalysts. TOC removal efficiency for Al2O3 without electron scavengers in an acidic condition was higher than that in a neutral or alkaline condition. However, TOC removal efficiency for Al2O3 with S2O82- was higher in a neutral condition than in other pH conditions. This indicates that the pH of a solution plays a critical role in the catalytic oxidation performance by determining surface charges of catalysts and yield of reactive radicals produced from water radiolysis. In the radiocatalytic system, H2O2 enhances the oxidation performance of catalysts (Al2O3 and TiO2) over a wide pH range (3-11). Meanwhile, S2O82- is not suitable with Al2O3 in acidic conditions because of its strong adsorption onto Al2O3 in this study.

[Adsorption Properties of Magnetic Phosphorous Camellia Oleifera Shells Biochar to Sulfamethoxazole in Water].

Magnetic phosphorous biochar （MPBC） was prepared from Camellia oleifera shells using phosphoric acid activation and iron co-deposition. The materials were characterized and analyzed through scanning electron microscopy （SEM）， X-ray diffractometry （XRD）， specific surface area and pore size analysis （BET）， Fourier infrared spectroscopy （FT-IR）， and X-ray photoelectron spectroscopy （XPS）. MPBC had a high surface area （1 139.28 m2·g-1） and abundant surface functional groups， and it could achieve fast solid-liquid separation under the action of an external magnetic field. The adsorption behavior and influencing factors of sulfamethoxazole （SMX） in water were investigated. The adsorbent showed excellent adsorption properties for SMX under acidic and neutral conditions， and alkaline conditions and the presence of CO32- had obvious inhibition on adsorption. The adsorption process conformed to the quasi-second-order kinetics and Langmuir model. The adsorption rate was fast， and the maximum adsorption capacity reached 356.49 mg·g-1. The adsorption process was a spontaneous exothermic reaction， and low temperature was beneficial to the adsorption. The adsorption mechanism was mainly the chemisorption of pyrophosphate surface functional groups （C-O-P bond） between the SMX molecule and MPBC and also included hydrogen bonding， π-π electron donor-acceptor （π-πEDA） interaction， and a pore filling effect. The development of MPBC adsorbent provides an effective way for resource utilization of waste Camellia oleifera shells and treatment of sulfamethoxazole wastewater.

Fate of sulfamethoxazole in wetland sediment under controlled redox conditions.

Redox condition is an important controlling factor for contaminant removal in constructed wetlands; however, the redox-sensitivity of antibiotic removal in wetland sediments under controlled conditions with specific electron acceptors remains unclear. Here, using a 14C radioactive tracer, we explored fate of sulfamethoxazole (SMX) in a wetland sediment slurry under oxic, nitrate-reducing, iron-reducing, and methanogenic conditions. In the sterile treatment, unlike the comparable SMX dissipation from the water phase under four redox conditions, non-extractable residues (NERs) of SMX was highest formed in the sediment under oxic condition, mainly in sequestered and ester/amide-linked forms. Microorganisms markedly promoted SMX transformation in the slurry. The dissipation rate of SMX and its transformation products (TPs) followed the order: oxic ≈ iron-reducing > methanogenic >> nitrate-reducing conditions, being consistent with the dynamics of microbial community in the sediment, where microbial diversity was greater and networks connectivity linking dominant bacteria to SMX transformation were more complex under oxic and iron-reducing conditions. Kinetic modeling indicated that the transformation trend of SMX and its TPs into the endpoint pool NERs depended on the redox conditions. Addition of wetland plant exudates and sediment dissolved organic matter at environmental concentrations affected neither the abiotic nor the biotic transformation of SMX. Overall, the iron-reducing condition was proven the most favorable and eco-friendly for SMX transformation, as it resulted in a high rate of SMX dissipation from water without an increase in toxicity and subsequent formation of significant stable NERs in sediment. Our study comprehensively revealed the abiotic and biotic transformation processes of SMX under controlled redox conditions and demonstrated iron-reducing condition allowing optimal removal of SMX in constructed wetlands.

Degradation products and transformation pathways of sulfamethoxazole chlorination disinfection by-products in constructed wetlands.

Antibiotics and available chlorine coexist in multiple aquatic environments, and thus antibiotics and their chlorinated disinfection by-products (Cl-DBPs) have been a great concern for the nature and human health. Herein, the degradation intermediates and transformation pathways of sulfamethoxazole (SMX) Cl-DBPs in constructed wetlands (CWs) were investigated. A total of five SMX Cl-DBPs and their twenty degradation products in CWs was identified in this study. SMX and its Cl-DBPs influenced the biodegradation rather than the adsorption process in CWs. S1 atom on sulfonyl group of SMX had the strongest nucleophilicity, and was most vulnerable for nucleophilic attack. N5 and N7 on amino groups, and C17 on the methyl group had great electronegativity, and were susceptible to electrophilic reactions. S1-N5 and S1-C8 bonds of SMX are the most prone to cleavage, followed by C11-N5, C16-C17, and C12-N7. The chlorination of SMX mainly occurred at S1, N5, and N7 sites, and went through S-C cleavage, S-N hydrolysis, and desulfonation. The biodegradation of SMX Cl-DBPs in CWs mainly occurred at S1, N5, N7, C8, and C17 sites, and went through processes including oxidation of methyl, hydroxyl and amino groups, desulfonation, decarboxylation, azo bond cleavage, benzene ring cleavage, ß-oxidation of fatty acids under the action of coenzymes. Over half of the SMX Cl-DBPs had greater bioaccumulation potential than their parent SMX, but the environmental risk of SMX Cl-DBPs was effectively reduced through the degradation by CWs.

Transformation process and phytotoxicity of sulfamethoxazole and N4-acetyl-sulfamethoxazole in rice.

Sulfonamide antibiotics, extensively used in human and veterinary therapy, accumulate in agroecosystem soils through livestock manure and sewage irrigation. However, the interaction between sulfonamides and rice plants remains unclear. This study investigated the transformation behavior and toxicity of sulfamethoxazole (SMX) and its main metabolite, N4-acetyl-sulfamethoxazole (NASMX) in rice. SMX and NASMX were rapidly taken up by roots and translocated acropetally. NASMX showed higher accumulating capacity, with NASMX concentrations up to 20.36 ± 1.98 µg/g (roots) and 5.62 ± 1.17 µg/g (shoots), and with SMX concentrations up to 15.97 ± 2.53 µg/g (roots) and 3.22 ± 0.789 µg/g (shoots). A total of 18 intermediate transformation products of SMX were identified by nontarget screening using Orbitrap-HRMS, revealing pathways such as deamination, hydroxylation, acetylation, formylation, and glycosylation. Notably, NASMX transformed back into SMX in rice, a novel finding. Transcriptomic analysis highlights the involvements of cytochrome P450 (CYP450), acetyltransferase (ACEs) and glycosyltransferases (GTs) in these biotransformation pathways. Moreover, exposure to SMX and NASMX disrupts TCA cycle, amino acid, linoleic acid, nucleotide metabolism, and phenylpropanoid biosynthesis pathways of rice, with NASMX exerting a stronger impact on metabolic networks. These findings elucidate the sulfonamides' metabolism, phytotoxicity mechanisms, and contribute to assessing food safety and human exposure risk amid antibiotic pollution.

Enzyme-induced reactive oxygen species trigger oxidative degradation of sulfamethoxazole within a methanotrophic biofilm.

Although microorganisms carrying copper-containing membrane-bound monooxygenase (CuMMOs), such as particulate methane monooxygenase (pMMO) and ammonia monooxygenase (AMO), have been extensively documented for their capability to degrade organic micropollutants (OMPs), the underlying reactive mechanism remains elusive. In this study, we for the first time demonstrate biogenic reactive oxygen species (ROS) play important roles in the degradation of sulfamethoxazole (SMX), a representative OMP, within a methane-fed biofilm. Highly-efficient and consistent SMX biodegradation was achieved in a CH4-based membrane biofilm reactor (MBfR), manifesting a remarkable SMX removal rate of 1210.6 ± 39.0 µg·L-1·d-1. Enzyme inhibition and ROS clearance experiments confirmed the significant contribution of ROS, which were generated through the catalytic reaction of pMMO and AMO enzymes, in facilitating SMX degradation. Through a combination of density functional theory (DFT) calculations, electron paramagnetic resonance (EPR) analysis, and transformation product detection, we elucidated that the ROS primarily targeted the aniline group in the SMX molecule, inducing the formation of aromatic radicals and its progressive mineralization. In contrast, the isoxazole-ring was not susceptible to electrophilic ROS attacks, leading to accumulation of 3-amino-5-methylisoxazole (3A5MI). Furthermore, microbiological analysis suggested Methylosarcina (a methanotroph) and Candidatus Nitrosotenuis (an ammonia-oxidizing archaea) collaborated as the SMX degraders, who carried highly conserved and expressed CuMMOs (pMMO and AMO) for ROS generation, thereby triggering the oxidative degradation of SMX. This study deciphers SMX biodegradation through a fresh perspective of free radical chemistry, and concurrently providing a theoretical framework for the advancement of environmental biotechnologies aimed at OMP removal.

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.

Vitamin C-regulated CoAl- layered double hydroxide with oxygen vacancies to efficiently activate peroxydisulfate for sulfamethoxazole removal triggered via reactive oxygen and high-valent cobalt species.

In this study, a vitamin C-regulated CoAl-layered double hydroxide with abundant oxygen vacancies was synthesized via a simple hydrothermal process. The resulting CoAl-layered double hydroxide was employed to activate peroxydisulfate for removal of sulfamethoxazole. The effect of the experimental parameters such as pH, catalyst dose and peroxydisulfate concentration on sulfamethoxazole removal was investigated. The current system exhibited excellent catalytic performance for sulfamethoxazole removal in a broad pH range (i.e., pH 3.0-11.0). Under the optimized condition, 94.2% of sulfamethoxazole was degraded within 15 min, accompanied by a 67.6% reduction in chemical oxygen demand. The effective sulfamethoxazole degradation could be attributed to four pathways. Firstly, the ≡ Co2+ in catalyst reacted with peroxydisulfate to generate reactive species, including SO4•-, •OH, O2•- and 1O2, which could degrade sulfamethoxazole. Secondly, the oxygen vacancies could modulate intrinsic electrons, resulted in the surface activation of catalyst and accelerated charge transfer, which was favorable for the degradation of sulfamethoxazole. Thirdly, the presence of vitamin C not only promoted the formation of oxygen vacancies but also expanded the interlayer spacing of layered double hydroxide. A large interlayer spacing facilitated the diffusion of peroxydisulfate and pollutants in the interlayer and improved the utilization efficiency of the active site. Lastly, the high-valent cobalt species exhibited excellent oxidation ability and enhanced the catalyst performance through continuously being employed as an electron acceptor. This study provided a valuable insight for the design and application of Co-based catalysts in peroxydisulfate-based advanced oxidation processes.

Boosted micropollutant removal over urchin-like structured hydroxyapatite-incorporated nickel magnetite catalyst via peroxydisulfate activation.

In this work, urchin-like structured hydroxyapatite-incorporated nickel magnetite (NiFe3O4/UHdA) microspheres were developed for the efficient removal of micropollutants (MPs) via peroxydisulfate (PDS) activation. The prepared NiFe3O4/UHdA degraded 99.0 % of sulfamethoxazole (SMX) after 15 min in 2 mM PDS, having a first-order kinetic rate constant of 0.210 min-1. In addition, NiFe3O4/UHdA outperformed its counterparts, i.e., Fe3O4/UHdA and Ni/UHdA, by giving rise to corresponding 3.6-fold and 8.6-fold enhancements in the SMX removal rate. The outstanding catalytic performance can be ascribed to (1) the urchin-like mesoporous structure with a large specific surface area and (2) the remarkable synergistic effect caused by the redox cycle of Ni3+/Ni2+ and Fe2+/Fe3+ that enhances multipath electron transfers on the surface of NiFe3O4/UHdA to produce more reactive oxygen species. Moreover, the effects of several reaction parameters, in this case the initial solution pH, PDS dosage, SMX concentration, catalyst loading, co-existing MPs and humic acid level on the catalytic performance of the NiFe3O4/UHdA + PDS system were systematically investigated and discussed in detail. The plausible catalytic mechanisms in the NiFe3O4/UHdA + PDS system were revealed via scavenging experiments and electron paramagnetic resonance analysis, which indicated a radical (•OH and SO4•-) as the major pathway and a nonradical (1O2) as the minor pathway for SMX degradation. Furthermore, NiFe3O4/UHdA exhibited fantastic magnetically separation and retained good catalytic activity with a low leached ion concentration during the performance of four cycles. Overall, the prepared NiFe3O4/UHdA with outstanding PDS activation could be a promising choice for the degradation of persistent organic pollutants from wastewater.

Critical Functions of Soil Components for In Situ Persulfate Oxidation of Sulfamethoxazole: Inherent Fe(II) Minerals-Coordinated Nonradical Pathway.

Naturally occurring iron (Fe) minerals have been proved to activate persulfate (PS) to generate reactive species, but the role of soil-inherent Fe minerals in activating PS as well as the underlying mechanisms remains poorly understood. Here, we investigated sulfamethoxazole (SMX) degradation by PS in two Fe-rich soils and one Fe-poor soil. Unlike with the radical-dominant oxidation processes in Fe-poor soil, PS was effectively activated through nonradical pathways (i.e., surface electron-transfer) in Fe-rich soils, accounting for 68.4%-85.5% of SMX degradation. The nonradical mechanism was evidenced by multiple methods, including electrochemical, in situ Raman, and competition kinetics tests. Inherent Fe-based minerals, especially those containing Fe(II) were the crucial activators of PS in Fe-rich soils. Compared to Fe(III) minerals, Fe(II) minerals (e.g., ilmenite) were more liable to form Fe(II) mineral-PS* complexes to initiate the nonradical pathways, oxidizing adjacent SMX via electron transfer. Furthermore, mineral structural Fe(II) was the dominant component to coordinate such a direct oxidation process. After PS oxidation, low-crystalline Fe minerals in soils were transformed into high-crystalline Fe phases. Collectively, our study shows that soil-inherent Fe minerals can effectively activate PS in Fe-rich soils, so the addition of exogenous iron might not be required for PS-based in situ chemical oxidation. Outcomes also provide new insights into the activation mechanisms when persulfate is used for the remediation of contaminated soils.

Overlooked role of void-nanoconfined effect in emerging pollutant degradation: Modulating the electronic structure of active sites to accelerate catalytic oxidation.

The efficient removal of emerging pollutant from water is the ultimate frontiers of advanced oxidation processes (AOPs), yet it is challenging to obtain higher catalytic activity and oxidation rate. Herein, a sustainable solution was proposed by optimizing the curvature of confined structure to modulate the electronic state of the active sites in nanochannels for improving the catalytic activity. In addition, the confined effect can enhance the oxidation rate by shorting the mass transfer of active species and pollutants. A void-nanoconfined nanoreactor was prepared by loading Fe2O3 into the nanochannels (<5 nm) of the hollow carbon sphere. An enhancement of 3 orders of magnitude was obtained in the degradation rate constant of void-nanoconfined catalytic system toward sulfamethoxazole (SMX) (6.25 min-1) compared with the non-confined system. The kinetics enhancement was attributed to the larger electron potential difference between the outer and inner nanochannel caused by the curvature increase of carbon sphere, accelerating the electron transfer, so that the energy barrier of SMX degradation reaction was reduced by 31 kcal/mol with the assistance of confinement energy. Importantly, the NC-IN/PDS system exhibited outstanding removal efficiency for the actual river water using a continuous flow reactor. This work provides a new insight into designing an efficient and stable catalytic nanoreactor, enriching the domain of advanced wastewater treatment strategies.

Facile synthesis of ball-milling and oxalic acid co-modified sludge biochar to efficiently activate peroxymonosulfate for sulfamethoxazole degradation: 1O2 and surface-bound radicals.

A novel approach of ball milling and oxalic acid was employed to modify sludge-based biochar (BOSBC) to boost its activation performance for peroxymonosulfate (PMS) towards efficient degradation of sulfamethoxazole (SMX). 98.6% of SMX was eliminated by PMS/BOSBC system within 60 min. Furthermore, PMS/BOSBC system was capable of maintaining high removal rates for SMX (>88.8%) in a wide pH range from 3 to 9, and displayed a high tolerance to background electrolytes including inorganic ions and humic acid (HA). Quenching experiments, electron paramagnetic resonance (EPR) analysis, in-situ Raman characterization and PMS decomposition experiments confirmed that the non-radicals of 1O2 and surface-bound radicals were the main contributors to SMX degradation by PMS/BOSBC system. The results of ecotoxicity assessment illustrated that all transformed products (TPs) generated in PMS/BOSBC system were less toxic than that of SMX. After five reuse cycles, PMS/BOSBC system still maintained a high removal rate for SMX (77.8%). Additionally, PMS/BOSBC system exhibited excellent degradation performance for SMX in various real waters (Yangtze River water (76.5%), lake water (74.1%), tap water (86.5%), and drinking water (98.1%)). Overall, this study provided novel insights on non-metal modification for sludge-based biochar and non-radical mechanism, and offered a feasible approach for municipal sludge disposal.

Starch of oat derived nanostructured Fe/Mn bimetallic carbon materials for sulfamethoxazole degradation via peroxymonosulfate activation.

Fe/Mn bimetallic carbon materials were synthesized by combining oat and urea, followed by and carbonization processes, the activity and mechanism of the obtained materials in activating peroxymonosulfate (PMS) for sulfamethoxazole (SMX) degradation were determined. Data suggested that the obtained material (CN@FeMn-10-800) showed the optimal performance for SMX degradation under the1:8:0.05:0.05 mass ratios of oat/urea/Fe/Mn. Around 91.2 % SMX (10 mg L-1) was removed under the conditions of 0.15 g L-1 CN@FeMn-10-800 and 0.20 g L-1 PMS. The CN@FeMn-10-800 showed great adaptability under different conditions, satisfactory activation repeatability and versatility. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) demonstrated that core-shell structure with rich porous of CN@FeMn-10-800 was achieved. Quenching test and electron paramagnetic resonance (EPR) indicated that surface bound oxygen and singlet oxygen (1O2) were the dominate reactive groups in this system. X-ray photoelectron spectroscopy (XPS) suggested that graphite N, Fe0, Fe3C and Mn(II) were the dominant active sites. Through the work, a simple strategy could be found to make high-value use of biomass and use it to effectively purified wastewater.

Bimetallic metal-organic framework as a high-performance peracetic acid activator for sulfamethoxazole degradation.

A novel 3D bimetallic metal-organic framework (MOF(Fe-Co)) was successfully prepared and its performance on sulfamethoxazole (SMX) removal in advanced oxidation process (AOP) based on peracetic acid (PAA) was evaluated. MOF(Fe-Co) exhibited an efficient catalytic performance on PAA activation for SMX degradation under neutral condition. Increasing PAA concentration could enhance SMX removal, while the variation of MOF(Fe-Co) dosage from 0.05 to 0.2 g/L had an inappreciable effect on SMX removal. According to the results of inductively coupled plasma mass spectrometry analyses and X-ray photoelectron spectroscopy, catalytic reactions mainly occurred on the surface of MOF(Fe-Co). Organic radicals (i.e., CH3C(O)OO• and CH3C(O)O•) were demonstrated to be the predominant reactive radicals for SMX degradation by MOF(Fe-Co)/PAA through radical quenching experiments. The presence of Cl- could enhance the degradation of SMX by MOF(Fe-Co)/PAA, while HCO3- and natural organic matter inhibited SMX degradation severely. Five identified degradation products were detected in this system and four possible SMX transformation pathways were proposed, including amino oxidation, S-N bond cleavage, coupling reaction and hydroxylation.