Construction of surface-rich MoS2 nanoflowers decorated on 2D layered MXene nanohybrid heterostructure for highly efficient and rapid degradation of oxytetracycline.

In this study, we successfully developed a hybrid architecture referred to as MoS2@MX, involving the integration of MoS2 layered onto MXene using a straightforward co-precipitation method. This innovative hybrid photocatalyst exhibited remarkable efficiency in removing oxytetracycline (OTC) molecules from aqueous solutions under visible-light irradiation. During the photocatalytic process, both MoS2 and MX played distinct yet complementary roles. MoS2 facilitated efficient electron transfer, while MX contributed to the generation of radicals. This unique collaboration resulted in a noteworthy 99 % oxidation efficiency for OTC degradation within a brief 60 min of visible light exposure in an aqueous environment. The radicals 1O2 and •OH were identified as the principal drivers behind OTC degradation, underscoring the vital role of the hybrid material. Mechanistically, the degradation of OTC involved several key steps, including C-H bond cleavage, de-carboxylation, C-N bond oxidation, and de-chlorination. Importantly, the MoS2@MX hybrid composite demonstrated remarkable stability, maintaining a noteworthy photocatalytic efficiency of 89 % for targeted OTC removal after undergoing five consecutive cycles. In conclusion, this study emphasizes the potential of the MoS2@MX hybrid material as an effective agent for degrading organic OTC compounds within aquatic environments. The hybrid's multifaceted roles and exceptional performance suggest promising applications in sustainable water treatment.

Tuning of interfacial HGO@CLS nanohybrid S-scheme heterojunction with improved carrier separation and photocatalytic activity towards RhB degradation.

Herein, we premeditated and invented the innovative hybrid photocatalyst 2D/2D CuLa2S4 on holey graphene oxide (HGO) (HGO@CLS) via the hydrothermal method. Electrochemical techniques demonstrate the action of HGO in the HGO@CLS photocatalyst as an effective medium for electron transfer. Combining bimetallic sulfides on porous HGO synergistically provides a higher negative conduction band edge (-0.141 V), greater photo response (10.8 mA/cm2), smaller charge transfer resistance (Rct = 1.79Ω), and lower photoluminescence (PL) spectral intensity. According to our research, the catalytic recitals are sped up when HGO is assimilated into CLS photocatalyst hetero-junction. Additionally, it lowers the reassimilation rate due to the combined mesh nanostructures and functionality of CLS and HGO. UV-Vis DRS, Mott-Schottky, PL, and Electrochemical impedance spectra (EIS) results manifested that the CuLa2S4/HGO makes the spatial separation competent and transference of charge carriers due to the photon irradiation and exhibits superior photocatalytic ability. Electron spin resonance (ESR) analysis confirmed that •OH and h+ were the predominant radical species responsible for Rhodamine B(RhB) degradation. Moreover, conceivable degradation ways of RhB were deduced according to the identified intermediates which are responsible for the degradation of recalcitrant products. To check the stability of the photocatalyst, revival tests were also carried out. Similarly, the oxidative byproducts created in the deprivation courses were looked at, and a thorough explanation for the mechanism of degradation was given.

Degradation of phenol by ball-milled activated carbon (ACBM) activated dual oxidant (persulfate/calcium peroxide) system: Effect of preadsorption and sequential injection.

This study explored pre-adsorption and sequential injection of dual oxidant (DuOx) of persulfate (PS) and calcium peroxide (CP) for phenol degradation in an aqueous solution. Ball-milled activated carbon (ACBM) was used as the catalyst in the following systems: pre-adsorption and sequential injection of PS and CP (ACBM + PS + CP), pre-adsorption and simultaneous injection of PS and CP (ACBM + PS/CP), simultaneous injection of ACBM, PS, and CP (ACBM/PS/CP), simultaneous injection of ACBM and PS (ACBM/PS), and simultaneous injection of ACBM and CP (ACBM/CP). The ACBM had a larger specific surface area, more graphitic structures, and more defects. Moreover, it showed better phenol removal when introduced simultaneously with PS and CP. The phenol removal was most the efficient in ACBM + PS + CP (98.8%) with a near-neutral final pH, followed by ACBM + PS/CP, ACBM/PS, ACBM/PS/CP, and ACBM/CP. This indicates that pre-adsorption and separate injection of PS and CP were the key strategy for improved performance and maintained favorable pH for the activation of PS and CP. The dual oxidant system (PS/CP) is superior to single oxidant systems (PS or CP). Scavenger experiments and the electron spin resonance spectra (ESR) demonstrated that non-radical species (1O2) were dominantly involved in ACBM + PS + CP, but radical species (HO•, SO4•-) also contributed. HCO3- and HPO42- inhibited phenol degradation in ACBM + PS + CP, whereas Cl- and HA had negligible effects. The ACBM + PS + CP showed high total organic carbon removal and ACBM was recyclable with a slight decrease in activity. This work is important as it provides a detailed insight into the strategy of pre-adsorption and sequential injection of dual oxidants for a practical and cost-effective method of groundwater remediation.

Enhanced Adsorption of Tetracycline by Thermal Modification of Coconut Shell-Based Activated Carbon.

Tetracycline (TC) is one of the most frequently detected antibiotics in various water matrices, posing adverse effects on aquatic ecosystems. In this study, coconut shell-based powdered activated carbon (PAC) was thermally modified under various temperatures to enhance TC adsorption. The PAC subjected to 800 °C (PAC800) showed the best TC adsorption. PAC and PAC800 were characterized using N2 adsorption/desorption isotherm, X-ray photoelectron spectroscopy, Raman spectroscopy, XRD, Boehm titration, and zeta potential analyses. Increases in the specific surface area, C/O ratio, C=O, surface charge, basic groups, and the number of stacked graphene layers along with a decrease in structural defects were observed for PAC800 compared to PAC. The TC adsorption was significantly improved for PAC800 compared to that of PAC, which is attributable to the enhanced electrostatic attraction and π-π EDA interactions induced by the changes in the properties. The Freundlich isotherm was the best fit indicating the heterogeneous nature, and the Freundlich constant of PAC and PAC800 increased from 85.8 to 119.5 and 132.1 to 178.6 (mg/g)‧(L/mg)1/n, respectively, when the temperature was increased from 296.15 to 318.15 K. The kinetics were well described by the pseudo-second-order adsorption model and the rate constant of PAC and PAC800 increased from 0.80 to 1.59 and from 0.72 to 1.29 × 10-3 g/mg‧min, respectively, as the temperature was increased. The activation energy of PAC and PAC800 was 23.7 and 19.6 J/mol, respectively, while the adsorption enthalpy was 196.7 and 98.5 kJ/mol, respectively, indicating endothermic nature. However, it was suggested that TC adsorption onto PAC800 was more favorable and was more contributed to by physisorption than that onto PAC. These results strongly suggest that the properties, adsorption capacity, and adsorption mechanisms of carbonaceous adsorbents can be significantly changed by simple thermal treatment. More, the results provide valuable information about the design of carbonaceous adsorbents with better performance where the structures and functional groups, which positively affect the adsorption, must be improved.

Changes in the catalytic activity of oxygen-doped graphitic carbon nitride for the repeated degradation of oxytetracycline.

Metal-free carbonaceous catalysts have gained growing interest because of their excellence in organic pollutant degradation. However, most of them suffer from deactivation after use, and the origins have not been investigated or understood. In this study, the changes in the characteristics after multiple uses of a carbonaceous catalyst, i.e., oxygen-doped graphitic carbon nitride (O-gCN), were investigated to identify the key factors affecting its reactivity. The O-gCN was repeatedly used to remove an antibiotic (oxytetracycline, OTC) in the presence of peroxymonosulfate (PMS). OTC removal was significantly reduced as the O-gCN was repeatedly used. The reactivity of O-gCN used five times (O-gCN5) corresponded well with the decreased signals of DMPO-X, DMPO-O2•-, and TEMP-1O2 in electron paramagnetic resonance spectra. These signal changes were accompanied by a shift of the involved reactive species from 1O2 and OH• for O-gCN to 1O2 and SO4•- for O-gCN5. The changes in activity and involved reactive species were attributed to the changes in the properties of O-gCN, considering the negligible OTC adsorption and slight PMS consumption. The results of X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy showed a decrease in the degree of defects, graphene-like layers, and crystallinity in graphitic structures, but an increase in the fractions of N and O, for O-gCN5. However, the OTC degradation pathways and intermediates were not significantly different for O-gCN and O-gCN5. These results provide valuable information for developing strategies for the design, practical use, and regeneration of carbonaceous catalysts.

Degradation of phenol using Fe(II)-activated CaO2: effect of ball-milled activated carbon (ACBM) addition.

In-situ chemical oxidation (ISCO) based on peroxide activation is one of the most promising technologies for removing organic contaminants from natural groundwater (NGW). However, use of the most common form of hydrogen peroxide (H2O2) is limited owing to its significantly rapid reaction rate and heat generation. Therefore, in the present study, the activation of calcium peroxide (CaO2), a slow H2O2 releasing agent, by Fe(II) was proposed (CaO2/Fe(II)), and the phenol degradation mechanisms and feasibility of NGW remediation were investigated. The optimum molar ratio of [phenol]/[CaO2]/[Fe(II)] (phenol = 0.5 mM) was 1/10/10, resulting in 87.0-92.5% phenol removal within 120 min under a broad initial pH range of 3-9. HCO3-, PO43-, and humic acid significantly inhibited degradation, whereas the effects of Cl-, NO3-, and SO42- were negligible. Reactive oxygen species (ROS) were identified based on the results of phenol degradation in the presence of scavengers and electron spin resonance (ESR) spectroscopy, which demonstrated that 1O2 played the dominant role, supported by •OH, in CaO2/Fe(II). Phenol removal in NGW (67.81%) was less than that in distilled and deionized water (DIW, 92.5%) at a [phenol]/[CaO2]/[Fe(II)] ratio of 1/10/10. However, phenol removal was significantly improved (∼100%) by increasing the CaO2 and Fe(II) doses to 1/20/20-40. Furthermore, when 125-250 mg L-1 of ball-milled activated carbon (ACBM) was added (CaO2/Fe(II)-ACBM), phenol removal was enhanced from 67.81% to 90.94-100% in the NGW. CaO2/Fe(II)-ACBM exhibited higher total organic carbon (TOC) removal than CaO2/Fe(II). In addition, no notable by-products were detected using CaO2/Fe(II)-ACBM, whereas the polymerisation products of hydroxylated and/or ring-cleaved compounds, that is, aconitic acid, gallocatechin, and 10-hydroxyaloin, were found in the reaction with CaO2/Fe(II). These results strongly suggest that CaO2/Fe(II)-ACBM is highly promising for groundwater remediation, minimizing degradation byproducts and the adverse effects caused by the NGW components.

Highly efficient degradation of phenolic compounds by Fe(II)-activated dual oxidant (persulfate/calcium peroxide) system.

This study demonstrates the feasibility, reaction mechanisms, and potential of practical applications of a dual oxidant (DuOx) system comprising calcium peroxide (CP) and persulfate (PS) catalyzed using Fe(II) [PS/CP/Fe(II)]. The DuOx system was superior in phenol degradation to single oxidant systems, i.e., PS/Fe(II) or CP/Fe(II), with 95.5% phenol removal under an optimum condition of a phenol/PS/CP/Fe(II) molar ratio of 1/1/5/6 ([Phenol]0=0.5 mM). Based on scavenger studies and electron spin resonance (ESR) spectroscopy, the phenol removal in the DuOx system was barrierless, with negative activation energy assisted by robust reactive species. The phenol degradation results in the presence of methanol, t-butanol, l-histidine, and NaN3. The ESR spectroscopy indicates that phenol degradation is attributed dominantly to 1O2 generated by recombining O2•- and radicals, such as hydroxyl (HO•) and sulfate (SO4•-). The performance of the DuOx system was highly efficient in pH 3-11, up to 10 mM Cl-, SO42-, or NO3-, and up to 50 mg/L humic acids but was strongly suppressed by more than 10 mM HCO3- and H2PO4-. In addition, the DuOx system was efficient in phenol removal in natural groundwater as well as removing and mineralizing other phenolic compounds (PCs) such as bisphenol A, chlorophenol, dichlorophenol, trichlorophenol, and nitrophenol. These results provide insights into the reactions induced by the DuOx system and confirm its applicability of in situ chemical oxidation in refractory organic pollutants.

Catalytic degradation of acetaminophen by Fe and N Co-doped multi-walled carbon nanotubes.

An Fe and N co-doped carbon nanotube (CNT) (Fe/N-CNT) was successfully prepared using a simple hydrothermal method. CNT, Fe doped CNTs (Fe-CNT), N doped CNTs (N-CNT), and Fe/N-CNT were characterized using scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and zeta potential analysis. The catalytic activities of the materials were investigated via pharmaceutical (acetaminophen, ACT) degradation using persulfate (PS). The ACT removal rate was in the order: Fe-CNT > N-CNT > Fe-CNT > CNT, for 30 min with 10 mg/L ACT, 0.05 g/L materials, and 0.08 mM PS. The doped N existed as pyridinic-N, pyrrolic-N/N-Fe, graphitic-N, and oxidized-N, while the doped Fe existed as Fe-N, FeO/Fe3O4, and Fe2O3/FeOOH at the edge. The rates of ACT removal and PS decomposition were well correlated with pyrrolic-N/N-Fe. The ACT removal in the Fe/N-CNT + PS system was as high as >98.4% and was not significantly affected by the initial pH of 2.0-8.2 and ten consecutive uses. However, natural organic matter (NOM) inhibited ACT removal by the accumulation on Fe/N-CNT. The results of ACT removal in the presence of radical scavengers, PS decomposition, and cyclic voltammetry showed that the ACT removal was dominantly attributed to a non-radical pathway with the accelerated electron transfer from ACT to PS through the Fe/N-CNT. The results in this study strongly suggest that the Fe/N-CNT + PS system is an excellent process for the degradation of refractory organic pollutants in various water matrices with improved performance and stability attributed by non-radical pathway.

Road-deposited sediments mediating the transfer of anthropogenic organic matter to stormwater runoff.

It has been regarded that road-deposited sediment (RDS) is one of the important sinks of anthropogenic pollutants as well as the major source of pollutants in stormwater runoff. However, the role of RDS, as a mediator of pollutants to the stormwater runoff, has not yet been investigated so far. Therefore, in this study, the leaching of dissolved pollutants, especially dissolved organic matter (DOM) from RDS, in synthetic precipitation was investigated. A significant amount of metals, nutrients, dissolved compounds, and DOM was leached. The leaching of DOM during 10 sequential leachings was 1811.3 and 2301.7 mg C/kg for larger (63 µm-2 mm) and smaller (< 63 µm) RDS, respectively. The results of UV/Vis spectroscopy, fluorescence spectroscopy, and size exclusion chromatography showed that the leached DOM was of anthropogenic/abiotic origins with lower molecular weight and humification degree. It is ubiquitous in stormwater runoff and industrial discharges and differs from natural organic matter. The results strongly suggest that RDS is an important mediator transferring anthropogenic pollutants to stormwater runoff. In addition, the removal of RDS, such as sweeping, would significantly reduce the pollutants input to the runoff.

Efficient removal of 17α-ethinylestradiol from secondary wastewater treatment effluent by a biofilm process incorporating biogenic manganese oxide and Pseudomonas putida strain MnB1.

This study proposes a biofilm process to immobilize biogenic manganese oxide (BMO) and Pseudomonas putida MnB1 (BMO-MnB1), which shows excellent synergistic effects for 17α-ethinylestradiol (EE2) from secondary wastewater treatment effluent (WWTE). Modified granular activated carbon (M-GAC) was used as the packing carrier, inoculated with Pseudomonas putida MnB1 and Mn(II) to form the BMO-MnB1 biofilm. Feasibility tests were performed to compare the EE2 removal efficiency with that of the conventional biofilm process (BAC) for heterogeneous microbial communities. Results show that in the BAC, EE2 was removed mainly by adsorption, with biodegradation contributing only slightly to the overall performance. In contrast, the BMO-MnB1 biofilter outperformed the BAC. Furthermore, less than 4% of the total EE2 removed was extracted from the biofilter medium over 150 days of operation, confirming that EE2 was biodegraded by P. putida MnB1 or chemically oxidized by BMO. Our results suggest that BMO-MnB1 biofilm processes have high potential for practical applications in removal of endocrine disrupting compounds from wastewater effluent.

Advanced oxidative degradation of acetaminophen by carbon catalysts: Radical vs non-radical pathways.

Two representative carbon catalysts, granular activated carbon (GAC) and carbon nanotube (CNT) were selected for the degradation of acetaminophen (ACT) by persulfate (PS) activation. In this study, the materials characterization study indicated that the surface functional groups and surface area of the GAC were more abundant and larger, respectively, than the CNT. Whereas the contribution of sp2 and CO groups of the CNT was superior to the GAC; the structural defect levels and surface charging characteristics (pHPZC) were similar in both. The mass-based pseudo-first-order reaction rate constant of the CNT was 1.5 m-1 g-1, which was 50 times higher than that of the GAC (0.03 m-1 g-1). Radical and non-radical pathways were evaluated for catalytic reactions by the GAC/PS and CNT/PS systems, respectively. Experimental results using scavenger tests, linear voltammetry, and electron spin resonance (ESR) showed that the radical pathway was dominant in the GAC/PS system, whereas the non-radical pathway was dominant in the CNT/PS systems. To confirm this, the influence of affecting factors such as initial ACT concentration, the dosage of oxidant (PS), and initial pH were also investigated and compared for the two systems. The results showed that the catalytic activity of the GAC/PS system was highly dependent on initial concentrations of ACT and PS, while these were less influential in the CNT/PS system. The removal efficiency of ACT was not affected under a pH of 3-7 in both systems. Reusability experiments were conducted five times, and both the CNT/PS and GAC/PS systems demonstrated that the removal rate of ACT did not notably decrease with the number of experiment repetitions. This means that the application of a carbon catalyst to treat pharmaceutical contaminants in wastewater is effective.

Controlled formation of magnetic yolk-shell structures with enhanced catalytic activity for removal of acetaminophen in a heterogeneous fenton-like system.

Encapsulating magnetic nanoparticles in a silica shell is a promising approach in many research fields. We recently demonstrated that the magnetic yolk-shell structure of Fe3O4@SiO2, which consists of an inner magnetite core and outer silica shell separated by a hollow void space, and its modified counterparts can be used as an effective catalyst for removal of acetaminophen in a heterogeneous Fenton-like reaction. The present study develops this approach further in an effort to design an effective procedure for preparing an optimum yolk-shell structure capable of greater catalytic performance. We investigated the use of a controlled synthesis strategy to fabricate an Fe3O4@SiO2 yolk-shell structure under varying conditions. Our focus was a single-step process that examines the effects of Stöber solution temperature, tetraethyl orthosilicate (TEOS) and hexadecyltrimethylammonium bromide (CTAB) concentrations, ethanol and water volume ratio, incubation time, and temperature on Fe3O4@SiO2 textural morphologies. The catalytic performance of the prepared materials was evaluated through oxidative degradation of acetaminophen in a heterogeneous Fenton-like reaction. Field emission transmission electron microscopy observation showed that magnetic yolk-shell structures with appropriate diameter, shell thickness, and hollow void space could be generated through tight control of synthesis conditions. Particle size and hollow void space increased when TEOS concentration increased from 22.10 to 88.50 mM. Hollow void space also increased as incubation time increased from 24 h to 72 h or incubation temperature increased from 50 to 90 °C. However, a yolk-shell structure did not form at a TEOS concentration of 11.10 mM, an incubation time of 3 h, or with an inappropriate ratio of ethyl alcohol and deionized water. Catalytic activity for degradation of acetaminophen increased with increasing hollow void space and thinning silica shell. In addition, the selected appropriate materials exhibited effective catalytic performance over five cycles of regeneration. This study demonstrates the significance of controlling the formation of yolk-shell structures, which enabled us to produce Fe3O4@SiO2 yolk-shell structures of desired and predictable size, hollow void space volume, and shell thickness for higher catalytic performance in degradation of pharmaceuticals in heterogeneous Fenton-like systems.

Reduction of non-point source contaminants associated with road-deposited sediments by sweeping.

Road-deposited sediments (RDS) on an expressway, residual RDS collected after sweeping, and RDS removed by means of sweeping were analyzed to evaluate the degree to which sweeping removed various non-point source contaminants. The total RDS load was 393.1 ± 80.3 kg/km and the RDS, residual RDS, and swept RDS were all highly polluted with organics, nutrients, and metals. Among the metals studied, Cu, Zn, Pb, Ni, Ca, and Fe were significantly enriched, and most of the contaminants were associated with particles within the size range from 63 µm to 2 mm. Sweeping reduced RDS and its associated contaminants by 33.3-49.1% on average. We also measured the biological oxygen demand (BOD) of RDS in the present work, representing to our knowledge the first time that this has been done; we found that RDS contains a significant amount of biodegradable organics and that the reduction of BOD by sweeping was higher than that of other contaminants. Significant correlations were found between the contaminants measured, indicating that the organics and the metals originated from both exhaust and non-exhaust particles. Meanwhile, the concentrations of Cu and Ni were higher in 63 µm-2 mm particles than in smaller particles, suggesting that some metals in RDS likely exist intrinsically in particles, rather than only as adsorbates on particle surfaces. Overall, the results in this study showed that sweeping to collect RDS can be a good alternative for reduction of contaminants in runoff.

Oxidative degradation of the antibiotic oxytetracycline by Cu@Fe3O4 core-shell nanoparticles.

A core-shell nanostructure composed of zero-valent Cu (core) and Fe3O4 (shell) (Cu@Fe3O4) was prepared by a simple reduction method and was evaluated for the degradation of oxytetracycline (OTC), an antibiotic. The Cu core and the Fe3O4 shell were verified by X-ray diffractometry (XRD) and transmission electron microscopy. The optimal molar ratio of [Cu]/[Fe] (1/1) in Cu@Fe3O4 created an outstanding synergic effect, leading to >99% OTC degradation as well as H2O2 decomposition within 10min at the reaction conditions of 1g/L Cu@Fe3O4, 20mg/L OTC, 20mM H2O2, and pH3.0 (and even at pH9.0). The OTC degradation rate by Cu@Fe3O4 was higher than obtained using single nanoparticle of Cu or Fe3O4. The results of the study using radical scavengers showed that OH is the major reactive oxygen species contributing to the OTC degradation. Finally, good stability, reusability, and magnetic separation were obtained with approximately 97% OTC degradation and no notable change in XRD patterns after the Cu@Fe3O4 catalyst was reused five times. These results demonstrate that Cu@Fe3O4 is a novel prospective candidate for the pharmaceutical and personal care products degradation in the aqueous phase.

Cu@Fe3O4 core-shell nanoparticle-catalyzed oxidative degradation of the antibiotic oxytetracycline in pre-treated landfill leachate.

Novel Cu@Fe3O4 core-shell nanoparticles prepared via a simple reduction method were evaluated for degradation of oxytetracycline (OTC) in pre-treated leachate (Lp-TREA) (leachate treated by conventional methods). Changes in the characteristics of dissolved organic matter (DOM) in the leachate were also investigated to gain a better understanding of the effects of DOM on the performance of Cu@Fe3O4. An excellent OTC degradation of >99% was achieved within 30 min under conditions of 1 g/L Cu@Fe3O4, 20 mg/L OTC, 20 mM H2O2, and initial pH 3.0, which was similar to the efficiency obtained in deionized water (90% even at pH 9.05). Humic acid (HA) and fulvic acid (FA) were completely degraded at initial pH 3, while aromatic protein (AP) with 32.7% of 1-3 kDa constituents were totally transformed to 0.5-1 kDa compounds, and 17% < 0.5 kDa material was degraded. The OTC removal rate decreased gradually as Cu@Fe3O4 was repeatedly used, but it was significantly enhanced when Cu@Fe3O4 was washed after five uses to remove the organic matter on its surface. The results suggest that Cu@Fe3O4 is a promising and effective catalyst for pharmaceutical and personal care product degradation in landfill leachates.

Synergistic effects of biogenic manganese oxide and Mn(II)-oxidizing bacterium Pseudomonas putida strain MnB1 on the degradation of 17 α-ethinylestradiol.

While biogenic manganese oxide (BMO) generated via the oxidation of Mn(II) by the Mn-oxidizing bacteria (MOB) have received attention, the relative roles of biological activity by MOB themselves were not clearly investigated. In this study, the synergistic effects of BMO and MOB Pseudomonas putida strain MnB1 on the degradation of 17α-ethinylestradiol (EE2) was investigated. Experiments with BMO in the presence of P. putida MnB1 showed 15-fold higher removal than that with BMO alone, suggesting that EE2 degradation was mediated by the biological activity of MOB as well as abiotic reaction by BMO. Trapping experiments with pyrophosphate (PP) proved that Mn(III) intermediate formed during the biological process from Mn (II) to Mn (IV) contribute much to the EE2 removal. Also, sharp decreases in EE2 removal were observed when microbial activity was inactivated by heat treatment or sodium azide. From this study, the EE2 removal mechanisms by BMO in the presence P. putida MnB1 are described as follows: (1) abiotic oxidation of EE2 by BMO occurs. (2) P. putida MnB1 indirectly oxidizes EE2 by transferring electrons from the Mn (III) intermediate. (3) P. putida MnB1 continuously re-oxidizes the Mn(II) released from the oxidative degradation of EE2 by BMO, generating new Mn(III)-intermediates or BMO.

Nonsacrificial Template Synthesis of Magnetic-Based Yolk-Shell Nanostructures for the Removal of Acetaminophen in Fenton-like Systems.

Recently, yolk-shell structured materials with active metal cores have received considerable attention in heterogeneous Fenton-like systems, which have excellent catalytic performance. In this study, we initially attempted the nonsacrificial template synthesis of yolk-shell structured nanoparticles with magnetite cores encapsulated in a mesoporous silica shell (Fe3O4@SiO2) via a modified sol-gel process and then evaluated their catalytic activity for acetaminophen degradation in Fenton-like systems. Second, copper nanoparticles were decorated on the surface of the Fe3O4@SiO2 microspheres (Fe3O4@SiO2@Cu) to enhance the catalytic activity. The morphological, structural, and physicochemical properties of the prepared materials were characterized via X-ray diffraction, X-ray photoelectron spectroscopy, field emission scanning electron microscopy, field emission transmission electron microscopy, nitrogen adsorption-desorption isotherms, specific surface area, ζ-potential, magnetic properties, and Fourier transform infrared spectroscopy. The results demonstrated a successful fabrication of the targeted materials. The yolk-shell structured materials possess a spherical morphology with an active core, protective shell, and hollow void. The Fe3O4@SiO2 and Fe3O4@SiO2@Cu variants showed acetaminophen removal rates significantly higher compared to those of their counterparts, i.e., the Fe3O4 and Fe3O4@Cu core-shell structures. Fe3O4@SiO2@Cu showed that the copper nanoparticles were firmly immobilized on the mesoporous silica shell, dramatically improving the catalytic performance. Both the yolk-shell structured Fe3O4@SiO2 and Fe3O4@SiO2@Cu exhibited good separation and satisfactory regeneration properties, which could be recycled six times without any obvious decline in catalytic activity. Overall, the results of this study suggested that Fe3O4@SiO2 and Fe3O4@SiO2@Cu yolk-shell nanostructures could be promising catalysts for a heterogeneous Fenton-like system by which the removal of emerging contaminants can be greatly improved.

Pollutant characteristics of road deposited sediments collected by road sweeping.

Road deposited sediments (RDS) swept from highways in South Korea were characterized to quantitatively evaluate the reduction in non-point source pollutants by sweeping. The swept RDS consisted primarily of sand (63 µm to 2 mm) particles (80.34 ± 8.33% of total weight) highly contaminated by organics, nutrients and heavy metals. The average concentrations of total organic carbon (TOC), biochemical oxygen demand (BOD), volatile solids (VS), total nitrogen (T-N), and total phosphorus (T-P) were 20.17 ± 9.13, 1.04 ± 0.62, 39.92 ± 16.55, 1.99 ± 0.96, and 0.54 ± 0.19 g kg(-1) (±one standard deviation), respectively, for 63 µm to 2 mm RDS. The concentrations of the pollutants were high for RDS smaller than 63 µm, but most of the mass was associated with the 63 µm to 2 mm RDS. The results suggest that the pollutants associated with RDS swept from highways originated mainly from engine wear, exhaust emissions, and tire wear. These results were different from the RDS on roads in residential and commercial areas, where natural particles and brake wear contribute significantly to RDS. In addition, the reductions in TOC, BOD, VS, T-N, T-P, Cu, Pb, Zn, Fe, and As based on the swept RDS measurements were calculated to be 3,355.3, 175.1, 6,621.4, 323.0, 88.3, 30.3, 13.7, 1.0, 303.4, 11,198.7, and 0.4 g km(-1), respectively.

Effects of ozonation and coagulation on effluent organic matter characteristics and ultrafiltration membrane fouling.

Effluent organic matter (EfOM) is the major cause of fouling in the low pressure membranes process for wastewater reuse. Coagulation and oxidation of biological wastewater treatment effluent have been applied for the fouling control of microfiltration membranes. However, the change in EfOM structure by pre-treatments has not been clearly identified. The changes of EfOM characteristics induced by coagulation and ozonation were investigated through size exclusion chromatography, UV/Vis spectrophotometry, fluorescence spectrophotometry and titrimetric analysis to identify the mechanisms in the reduction of ultrafiltration (UF) membrane fouling. The results indicated that reduction of flux decline by coagulation was due to modified characteristics of dissolved organic carbon (DOC) content. Total concentration of DOC was not reduced by ozonation. However, the mass fraction of the molecules with molecular weight larger than 5 kDa, fluorescence intensity, aromaticity, highly condensed chromophores, average molecular weight and soluble microbial byproducts decreased greatly after ozonation. These results indicated that EfOM was partially oxidized by ozonation to low molecular weight, highly charged compounds with abundant electron-withdrawing functional groups, which are favourable for alleviating UF membrane flux decline.

Deactivation of nanoscale zero-valent iron by humic acid and by retention in water.

The effects of the deactivation of nanoscale zero-valent iron (NZVI), induced by humic acid (HA) and by the retention of NZVI in water, on nitrate reduction were investigated using a kinetic study. Both the nitrate removal and generation of ammonia were significantly inhibited as the HA adsorption amount and retention time were increased. However, HA removal was greatly enhanced when the NZVI was used after 1 d or 25 d of retention in water. The results are caused by the formation of iron oxides/hydroxides, which increased the specific surface area and the degree of NZVI aggregation which was observed by transmission electron microscopy (TEM). However, the nitrate reduction was greater at the beginning of reaction in the presence of HA when fresh NZVI was used, because of the enhanced electron transfer by the HA in bulk phase and on NZVI surface as train sequences. The pseudo second order adsorption kinetic equation incorporating deactivation and a Langmuir-Hinshelwood (LH) type kinetic equation provided accurate descriptions of the nitrate removal and ammonia generation, respectively. The deactivation constant and the reaction rate constant of the LH type kinetic equation were strongly correlated with the HA amount accumulated on NZVI. These results suggest that the HA accumulation on the NZVI surface reactive sites plays the dominant role in the inhibition and the inhibition can be described successfully using the deactivation model. The HA accumulation on NZVI was verified using TEM.