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Development of new technologies with strong selectivity for target pollutants and low sensitivity toward a water matrix remains challenging. Herein, we introduced a novel strategy that used chlorite as an activator for Mn(VII) at pH 4.8, turning the inert reactivity of the pollutants toward Mn(VII) into a strong reactivity. This paved a new way for triggering reactions in water decontamination. By utilizing sulfamethoxazole (SMX) as a typical pollutant, we proposed coupled pathways involving electron transfer across hydrogen bonds (TEHB) and oxidation by reactive manganese species. The results indicated that a hydrogen bonding complex, SMX-ClO2-*, formed through chlorite binding the amino group of SMX initially in the TEHB route; such a complex exhibited a stronger reduction capability toward Mn(VII). Chlorite, in the hydrogen bonding complex SMX-ClO2-*, can then complex with Mn(VII). Consequently, a new reactive center (SMX-ClO2--Mn(VII)*) was formed, initiating the transfer of electrons across hydrogen bonds and the preliminary degradation of SMX. This is followed by the involvement of the generated Mn(V)-ClO2-/Mn(III) in the reduction process of Mn(VII). Such a process showed pH-dependent degradation, with a removal ratio ranging from 80% to near-stagnation as pH increased from 4.8 to 7. Combining with pKa analysis showed that the predominant forms of contaminants were crucial for the removal efficiency of pollutants by the Mn(VII)/chlorite process. The impact of the water matrix was demonstrated to have few adverse or even beneficial effects. With satisfactory performance against numerous contaminants, this study introduced a novel Mn(VII) synergistic strategy, and a new reactivity pattern focused on reducing the reduction potential of the contaminant, as opposed to increasing the oxidation potential of oxidants.
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Despite the importance of surface iron (hydr)oxides (Fe-(hydr)oxides) for the decontamination performance of zerovalent iron (ZVI) -based technologies has been well recognized, controversial understandings of their exact roles still exist due to the complex species distribution of Fe-(hydr)oxides. Herein, we re-structured the surface of ZVI using eight distinct Fe-(hydr)oxides and analyzed their species-specific effects on the performance of ZVI for Se(IV) under well-controlled conditions. The kinetics-relevant performance indicators (Se(IV) removal rates, Fe2+ release rates, and the utilization ratio of ZVI) under the effect of each Fe-(hydr)oxide roughly followed the order: δ-FeOOH > Fe5HO8·4H2O > α-FeOOH > ß-FeOOH > γ-FeOOH > γ-Fe2O3 > Fe3O4 > α-Fe2O3. Multiple linear regression analysis shows that the large pore volume and size (instead of specific surface area), low open-circuit potential, and low electrochemical impedance are key positive properties for kinetics-relevant performance. Besides, for electron efficiency of ZVI, only Fe3O4 increased the value to 50.0%, due to the contribution of its ferrous components, while others did not change it (â¼20%). Additional experiments with commercial ZVI covered by individual Fe-(hydr)oxides confirmed the observed species-specific trends. All these results not only provide new basis for mechanism explanation but also have practical implications for the production or modification of ZVI.
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Cascading failures pose a significant security threat to networked systems, with recent global incidents underscoring their destructive potential. The security threat of cascading failures has always existed, but the evolution of cyber-physical systems (CPSs) has introduced novel dimensions to cascading failures, intensifying their threats owing to the intricate fusion of cyber and physical domains. Addressing these threats requires a nuanced understanding achieved through failure modeling and vulnerability analysis. By analyzing the historical failures in different CPSs, the cascading failure in CPSs is comprehensively defined as a complicated propagation process in coupled cyber and physical systems, initialized by natural accidents or human interference, which exhibits a progressive evolution within the networked structure and ultimately results in unexpected large-scale systemic failures. Subsequently, this study advances the development of instructions for modeling cascading failures and conducting vulnerability analyses within CPSs. The examination also delves into the core challenges inherent in these methodologies. Moreover, a comprehensive survey and classification of extant research methodologies and solutions are undertaken, accompanied by a concise evaluation of their advancements and limitations. To validate the performance of these methodologies, numerical experiments are conducted to ascertain their distinct features. In conclusion, this article advocates for future research initiatives, particularly emphasizing the exploration of uncertainty analysis, defense strategies, and verification platforms. By addressing these areas, the resilience of CPSs against cascading failures can be significantly enhanced.
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Electrochemical advanced oxidation processes (EAOPs) have shown great promise for treating industrial wastewater contaminated with phenolic compounds. However, the presence of chloride in the wastewater leads to the production of undesirable chlorinated organic and inorganic byproducts, limiting the application of EAOPs. To address this challenge, we investigated the potential of incorporating Fe(II) and Fe(III) into the EAOPs with a boron-doped diamond (BDD) anode under near-neutral conditions. Our findings revealed that both Fe(II) and Fe(III) facilitated the generation of high-valent iron-oxo species (Fe(IV) and Fe(V)) in the anodic compartment, thereby reducing the oxidation contribution of reactive chlorine species. Remarkably, the addition of 1000 µM Fe(II) under high chloride conditions resulted in over a 2.8-fold increase in the oxidation rate of 50 µM phenolic contaminants at pH 6.5. Furthermore, 1000 µM Fe(II) contributed to a reduction of more than 66% in the formation of chlorinated byproducts, consequently enhancing the biodegradability of the treated water. Additionally, transitioning from batch mode to continuous flow mode further amplified the positive effects of Fe(II) on the EAOPs. Overall, this study presents a modified electrochemical approach that simultaneously enhanced the degradation of phenolic contaminants and improved the biodegradability of wastewater with high chloride concentrations.
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Cloruros , Técnicas Electroquímicas , Hierro , Oxidación-Reducción , Fenoles , Aguas Residuales , Contaminantes Químicos del Agua , Aguas Residuales/química , Fenoles/química , Cloruros/química , Hierro/química , Contaminantes Químicos del Agua/química , Eliminación de Residuos Líquidos/métodos , Purificación del Agua/métodos , Electrodos , Boro/químicaRESUMEN
Humic acid (HA) is ubiquitous in natural aquatic environments and effectively accelerates decontamination by permanganate (Mn(VII)). However, the detailed mechanism remains uncertain. Herein, the intrinsic mechanisms of HA's impact on phenolics oxidation by Mn(VII) and its intermediate manganese oxo-anions were systematically studied. Results suggested that HA facilitated the transfer of a single electron from Mn(VII), resulting in the sequential formation of Mn(VI) and Mn(V). The formed Mn(V) was further reduced to Mn(III) through a double electron transfer process by HA. Mn(III) was responsible for the HA-boosted oxidation as the active species attacking pollutants, while Mn(VI) and Mn(V) tended to act as intermediate species due to their own instability. In addition, HA could serve as a stabilizer to form a complex with produced Mn(III) and retard the disproportionation of Mn(III). Notably, manganese oxo-anions did not mineralize HA but essentially changed its composition. According to the results of Fourier-transform ion cyclotron resonance mass spectrometry and the second derivative analysis of Fourier-transform infrared spectroscopy, we found that manganese oxo-anions triggered the decomposition of C-H bonds on HA and subsequently produced oxygen-containing functional groups (i.e., C-O). This study might shed new light on the HA/manganese oxo-anion process.
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Sustancias Húmicas , Manganeso , Oxidación-Reducción , Fenoles , Manganeso/química , Fenoles/química , Aniones , Compuestos de Manganeso/química , Óxidos/química , Contaminantes Químicos del Agua/químicaRESUMEN
Diatomic-site catalysts (DASCs) inherit the excellent performance of single-atom catalysts (SACs) by utilizing two adjacent atomic metal species to achieve functional complementarity and synergistic effects that improve the carbon dioxide reduction reaction (CO2RR) and H2 evolution reaction (HER) kinetics. Herein, we report a method to further improve the catalytic efficiency of Pt by using Pt and Ru single atoms randomly anchored on a g-C3N4 surface, yielding partial Pt-Ru dimers. The synthesized catalyst exhibits extraordinary photocatalytic activity and stability in both the CO2RR and HER processes. In-depth experimentation, the pH-dependent chemical exchange saturation transfer (CEST) imaging nuclear magnetic resonance (NMR) method, and theoretical analyses reveal that the excellent performance is attributed to orbital coupling between the Pt atoms and the neighboring Ru atoms (mainly dxy and dxz), which decreases the orbital energy levels and weakens the bond strength with intermediates, resulting in improved CO2RR and HER performance. This study successfully applies the pH-dependent CEST imaging NMR method to catalytic reactions, and CO2 adsorption is directly observed using CEST 2D imaging maps. This work presents significant potential for a variety of catalytic reaction applications by systematically designing bimetallic dimers with higher activity and stability.
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One of the most prevalent co-operative disorders is postoperative cognitive dysfunction (POCD), however, its pathogenesis remains unclear. Thus, the aim of this work was to evaluate SIRT3's impact on cognitive decline in aged mice under anesthesia. Adeno-associated virus SIRT3 vector (AAV-SIRT3) or empty vector (AAV-VEH) was injected into the hippocampal region of aged mice after sevoflurane induction in order to upregulate the expression of SIRT3. The expression levels of SIRT3, pro-inflammatory cytokines, and apoptotic factors in hippocampus tissues were identified by PCR, Western blotting, TUNEL staining, and enzyme-linked immunosorbent assay (ELISA), and the cognitive function of mice was assessed. The SIRT3 expression was down-regulated in the hippocampal tissue of anesthetized mice. SIRT3 overexpression can improve the learning and memory ability, reduce the escape latency, and increase the residence time in the platform and platform crossing ability of mice. The overexpression of SIRT3 in hippocampus can reduce the oxidative stress response and inflammatory response induced by anesthesia in mice, increase the superoxide dismutase (SOD) expression level, and decrease the expression level of MDA and inflammatory factors in hippocampus. In addition, SIRT3 overexpression can also reduce anesthetic-induced hippocampal cell apoptosis. By reducing the hippocampus mitochondrial oxidative stress response, SIRT3 plays a significant role in the pathophysiology of POCD in mice and is a potential target for POCD treatment and diagnosis.
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Disfunción Cognitiva , Complicaciones Cognitivas Postoperatorias , Sirtuina 3 , Animales , Ratones , Disfunción Cognitiva/genética , Estrés Oxidativo , Complicaciones Cognitivas Postoperatorias/genética , Sevoflurano/efectos adversos , Sevoflurano/farmacología , Sirtuina 3/genética , Sirtuina 3/metabolismoRESUMEN
Contrasting effects of sulfidation on contaminants reduction by zero-valent iron (ZVI) has been reported in literature but the underlying mechanisms remain unclear. Here, under well-controlled conditions, we compared the performance of ZVI and sulfidated ZVI (S-ZVI) toward a series of chlorinated compounds. Results revealed that, although S-ZVI was more reactive than ZVI toward hexachloroethane, pentachloroethane, tetrachloroethylene, and trichloroethene, sulfidation hindered the dechlorination of the other ten tested chlorinated aliphatics by a factor of 1.5-125. Moreover, S-ZVI may lead to an accumulation of toxic partially-dechlorinated products. Analogous to its effects on ZVI reactivity, sulfidation also exerted positive, negligible, or negative effects on the electron efficiency of ZVI. Solvent kinetic isotope effect analysis suggested that direct electron transfer rather than reaction with atomic hydrogen was the dominant reduction mechanism in S-ZVI system. Hence, the sulfidation enhancing effects could be expected only when direct electron transfer is the preferred reduction route for target contaminants. Furthermore, linear free energy relationships analysis indicated one-electron reduction potential could be used to predict the transformation of chlorinated ethanes by S-ZVI, whereas for chlorinated ethenes, their adsorption properties on S-ZVI determined the dechlorination process. All these findings may offer guidance for the decision-making regarding the application of S-ZVI.
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The selective transformation of organics from wastewater to value-added chemicals is considered an upcycling process beneficial for carbon neutrality. Herein, we present an innovative electrocatalytic oxidation (ECO) system aimed at achieving the selective conversion of phenols in wastewater to para-benzoquinone (p-BQ), a valuable chemical widely utilized in the manufacturing and chemical industries. Notably, 96.4% of phenol abatement and 78.9% of p-BQ yield are synchronously obtained over a preferred carbon cloth-supported ruthenium nanoparticles (Ru/C) anode. Such unprecedented results stem from the weak Ru-O bond between the Ru active sites and generated p-BQ, which facilitates the desorption of p-BQ from the anode surface. This property not only prevents the excessive oxidation of the generated p-BQ but also reinstates the Ru active sites essential for the rapid ECO of phenol. Furthermore, this ECO system operates at ambient conditions and obviates the need for potent chemical oxidants, establishing a sustainable avenue for p-BQ production. Importantly, the system efficacy can be adaptable in actual phenol-containing coking wastewater, highlighting its potential practical application prospect. As a proof of concept, we construct an electrified Ru/C membrane for ECO of phenol, attaining phenol removal of 95.8% coupled with p-BQ selectivity of 73.1%, which demonstrates the feasibility of the ECO system in a scalable flow-through operation mode. This work provides a promising ECO strategy for realizing both phenols removal and valuable organics recovery from phenolic wastewater.
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Benzoquinonas , Aguas Residuales , Contaminantes Químicos del Agua , Fenol/química , Fenoles , Carbono , Contaminantes Químicos del Agua/químicaRESUMEN
Despite decades of research on phenols oxidation by permanganate, there are still considerable uncertainties regarding the mechanisms accounting for the unexpected parabolic pH-dependent oxidation rate. Herein, the pH effect on phenols oxidation was reinvestigated experimentally and theoretically by highlighting the previously unappreciated proton transfer. The results revealed that the oxidation of protonated phenols occurred via proton-coupled electron transfer (PCET) pathways, which can switch from ETPT (electron transfer followed by proton transfer) to CEPT (concerted electron-proton transfer) or PTET (proton transfer followed by electron transfer) with an increase in pH. A PCET-based model was thus established, and it could fit the kinetic data of phenols oxidation by permanganate well. In contrast with what was previously thought, both the simulating results and the density functional theory calculation indicated the rate of CEPT reaction of protonated phenols with OH- as the proton acceptor was much higher than that of deprotonated phenols, which could account for the pH-rate profiles for phenols oxidation. Analysis of the quantitative structure-activity relationships among the modeled rate constants, Hammett constants, and pKa values of phenols further supports the idea that the oxidation of protonated phenols is dominated by PCET. This study improves our understanding of permanganate oxidation and suggests a new pattern of reactivity that may be applicable to other systems.
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Electrones , Protones , Concentración de Iones de Hidrógeno , Oxidación-Reducción , Transporte de Electrón , Fenoles , CinéticaRESUMEN
BACKGROUND: Premature ovarian insufficiency (POI) is an important cause of infertility characterized by the functional decline of the ovary. Granulosa cells (GCs) around oocytes are critical for folliculogenesis, and GC dysfunction is one of the important etiologies of POI. The aim of this study was to explore the potential biomarkers of POI by identifying hub genes and analyze the correlation of biomarkers with immune infiltration in POI using RNA profiling and bioinformatics analysis. METHODS: RNA sequencing was performed on GCs from biochemical POI (bPOI) patients and controls. Differential expression analysis and weighted gene co-expression network analysis (WGCNA) were used to explore the candidate genes. qRTâPCR was performed to verify the expression of hub genes. Western blot, Cell Counting Kit-8, 5-ethynyl-2'-deoxyuridine (EdU) assays, TUNEL (TdT-mediated dUTP Nick-End Labeling) and flow cytometry analysis were used to validate the possible role of ubiquitin-conjugating enzyme 2C (UBE2C) in POI. CIBERSORT was adopted to explore immune cell infiltration and the correlation between UBE2C and immune cells in bPOI. RESULTS: Through analysis of differentially expressed genes (DEGs) and WGCNA, we obtained 143 candidate genes. After construction of the proteinâprotein interaction (PPI) network and analysis with Cytoscape, 10 hub genes, including UBE2C, PBK, BUB1, CDC20, NUSAP1, CENPA, CCNB2, TOP2A, AURKB, and FOXM1, were identified and verified by qRTâPCR. Subsequently, UBE2C was chosen as a possible biomarker of POI because knockdown of UBE2C could inhibit the proliferation and promote the apoptosis of GCs. Immune infiltration analysis indicated that monocytes and M1 macrophages may be associated with the pathogenesis of POI. In addition, UBE2C was negatively correlated with monocytes and M1 macrophages in POI. CONCLUSIONS: This study identified a hub gene in GCs that might be important in the pathogenesis of POI and revealed the key role of UBE2C in driving POI. Immune infiltration may be highly related with the onset and etiology of POI.
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Menopausia Prematura , Insuficiencia Ovárica Primaria , Femenino , Humanos , Transcriptoma , Enzimas Ubiquitina-Conjugadoras/genética , Insuficiencia Ovárica Primaria/genética , Menopausia Prematura/genética , Células de la Granulosa , BiomarcadoresRESUMEN
Recent research has primarily focused on the utilization of reductants as activators for Fe(VI) to generate high-valent iron species (Fe(IV)/Fe(V)) for the degradation of emerging organic contaminants (EOCs). However, a significant drawback of this approach arises from the reaction between reductants and ferrates, leading to a decrease in oxidation capacity. This study introduces a novel discovery that highlights the potential of the iron(III)-(1,10-phenanthroline) (Fe(III)-Phen) complex as an activator, effectively enhancing the degradation of EOCs by Fe(VI) and augmenting the overall oxidation capacity of Fe(VI). The degradation of EOCs in the Fe(VI)/Fe(III)-Phen system is facilitated through two mechanisms: a direct electron transfer (DET) process and electron shuttle action. The DET process involves the formation of a Phen-Fe(III)-Fe(VI)* complex, which exhibits a stronger oxidation ability than Fe(VI) alone and can accept electrons directly from EOCs. On the other hand, the electron shuttle process utilizes Fe(III)-Phen as a redox mediator to transfer electrons from EOCs to Fe(VI) through the Fe(IV)/Fe(III) or Fe(IV)/Fe(II)/Fe(III) cycle. Moreover, the Fe(III)-Phen complex can improve the utilization efficiency of Fe(V) by preventing its self-decay. This study's findings may present a viable option for utilizing an effective catalyst to enhance the oxidation of EOCs by Fe(VI) and Fe(V).
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Contaminantes Químicos del Agua , Purificación del Agua , Compuestos Férricos , Electrones , Sustancias Reductoras , Oxidación-Reducción , HierroRESUMEN
Objective: In the past, obviously displaced lateral condyle fractures of the humerus in children were treated satisfactorily with open reduction and internal fixation (ORIF). However, in recent years, more studies have mentioned closed reduction and percutaneous pinning (CRPP) of these fractures. Methods: In this retrospective investigation, the radiographic and clinical results of patients with these fractures that were initially managed with CRPP were newly classified. We classified these fractures into three groups according to the degree and pattern of fracture displacement as identified on four radiographic images. In Type I, the fracture is unstable and displacement is ≥2 mm; In Type II degree I, the fracture is unstable and displacement is >2 mm, with single rotation of fragment; In Type II degree II, the fracture is unstable and displacement is >2 mm, with single rotation of fragment, with rotation of fragment and antero-proximal displacement; In Type III, the fracture is unstable and displacement is >2 mm, with posterior dislocation of elbow joint. We also designed an algorithm for closed reduction of these fractures according to this new classification. Results: We retrospectively analyzed the radiographic and clinical results of 37 unstable fractures (in 22 boys and 15 girls) that were treated with closed reduction. Twenty-one of 25 (84.0%) type I fractures, which could have been reduced to within 2 mm of residual displacement, were treated with closed reduction and pinning with 2 or 3 Kirschner wires (K wires). Three of 5 (60.0%) type II degree I, 3 of 4 (75.0%) type II degree II, and 3 of 3 (100%) type III fractures were treated with CRPP. In 4 of 25 (16.0%) type I, 2 of 5 (40.0%) type II degree I and 1 of 4 (25.0%) type II degree II fractures, closed reduction failed, so ORIF was implemented. There were no complications, such as nonunion, osteonecrosis of the capitellum, superficial or deep infection, malunion, cubitus varus or valgus, or early physeal arrest. Conclusion: Although the management of type III fractures may not be more difficult than type II fractures with a rotated fracture fragment, as elbow dislocations are usually easy reducible. This retrospective study showed that type III fractures should not be ignored as a lateral condyle fracture that can be cured with CRPP and that lateral humeral condyle fractures with obvious displacement and rotation can be initially treated with CRPP to achieve satisfactory recovery of the elbow. Kirschner wire (K wire) fixation is recommended to avoid reoperation or anesthesia for hardware removal.
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Attention has been long focused on enhancing permanganate (Mn(VII)) oxidation capacity for eliminating organic contaminants via generating active manganese intermediates (AMnIs). Nevertheless, limited consideration has been given to the unnecessary consumption of Mn(VII) due to the spontaneous disproportionation of AMnIs during their formation. In this work, we innovatively introduced green polyaspartic acid (PASP) as both reducing and chelating agents to activate Mn(VII) to enhance the oxidation capacity and utilization efficiency of Mn(VII). Multiple lines of evidence suggest that Mn(III), existing as Mn(III)-PASP complex, was generated and dominated the degradation of bisphenol A (BPA) in the Mn(VII)/PASP system. The stabilized Mn(III) species enabled Mn(VII) utilization efficiency in the Mn(VII)/PASP system to be higher than that in Mn(VII) alone. Moreover, the electrophilic Mn(III) species was verified to mainly attack the inclusive benzene ring and isopropyl group to realize BPA oxidation and its toxicity reduction in the Mn(VII)/PASP system. In addition, the Mn(VII)/PASP system showed the potential for selectively oxidizing organic contaminants bearing phenol and aniline moieties in real waters without interference from most of coexisting water matrices. This work brightens an overlooked route to both high oxidation capacity and efficient Mn(VII) utilization in the Mn(VII)-based oxidation processes.
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Mn(II) exhibits a superb ability in activating periodate (PI) for the efficient degradation of aqueous organic contaminants. Nevertheless, ambiguous conclusions regarding the involved reactive species contributing to the removal of organic contaminants remain unresolved. In this work, we found that the Mn(II)/PI process showed outstanding and selective reactivity for oxidizing sulfonamides with the removal ranging from 57.1% to 100% at pH 6.5. Many lines of evidence suggest that the in-situ formed colloidal MnO2 (cMnO2) served as a catalyst to mediate electron transfer from sulfonamides to PI on its surface via forming cMnO2-PI complex (cMnO2-PI*) for the efficient oxidation of sulfonamides in the Mn(II)/PI process. Experimental results and density functional theory (DFT) calculations verify that the inclusive aniline moiety was the key site determining the electron transfer-dominated oxidation of sulfonamides. Furthermore, DFT calculation results reveal that the discrepancies in the removal of sulfonamides in the Mn(II)/PI process were attributed to different kinetic stability and chemical reactivity of sulfonamides caused by their heterocyclic substituents. In addition, a high utilization efficiency of PI was achieved in the Mn(II)/PI process owing to the surface-mediated electron transfer mechanism. This work provides deep insights into the surface-promoted mechanism in the cMnO2-involved oxidation processes.
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Antibacterianos , Compuestos de Manganeso , Óxidos , Electrones , Oxidación-Reducción , Sulfanilamida , SulfonamidasRESUMEN
In this study, we introduce the count-based Morgan fingerprint (C-MF) to represent chemical structures of contaminants and develop machine learning (ML)-based predictive models for their activities and properties. Compared with the binary Morgan fingerprint (B-MF), C-MF not only qualifies the presence or absence of an atom group but also quantifies its counts in a molecule. We employ six different ML algorithms (ridge regression, SVM, KNN, RF, XGBoost, and CatBoost) to develop models on 10 contaminant-related data sets based on C-MF and B-MF to compare them in terms of the model's predictive performance, interpretation, and applicability domain (AD). Our results show that C-MF outperforms B-MF in nine of 10 data sets in terms of model predictive performance. The advantage of C-MF over B-MF is dependent on the ML algorithm, and the performance enhancements are proportional to the difference in the chemical diversity of data sets calculated by B-MF and C-MF. Model interpretation results show that the C-MF-based model can elucidate the effect of atom group counts on the target and have a wider range of SHAP values. AD analysis shows that C-MF-based models have an AD similar to that of B-MF-based ones. Finally, we developed a "ContaminaNET" platform to deploy these C-MF-based models for free use.
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Algoritmos , Aprendizaje Automático , Contaminación Química del Agua , Agua/química , Contaminación Química del Agua/análisisRESUMEN
Fe(IV) and Fe(V) are promising oxidants for the selective removal of emerging organic contaminants (EOCs) from water under near-neutral conditions. The Fe(III)-assisted electrochemical oxidation system with a BDD anode (Fe(III)-EOS-BDD system) has been employed to generate Fe(VI), while the generation and contributions of Fe(IV) and Fe(V) have been largely ignored. Thus, we examined the feasibility and involved mechanisms of the selective degradation of EOCs in the Fe(III)-EOS-BDD system under near-neutral conditions. It was found that Fe(III) application selectively accelerated the electro-oxidation of phenolic and sulfonamide organics and made the oxidation system be resistant to interference from Cl-, HCO3-, and humic acid. Several lines of evidence indicated that EOCs were decomposed via direct electron-transfer process on the BDD anode and by Fe(IV) and Fe(V) but not Fe(VI), besides HOâ¢. Fe(VI) was not generated until the exhaustion of EOCs. Furthermore, the overall contributions of Fe(IV) and Fe(V) to the oxidation of phenolic and sulfonamide organics were over 45%. Our results also revealed that Fe(III) was oxidized primarily by HO⢠to Fe(IV) and Fe(V) in the Fe(III)-EOS-BDD system. This study advances the understanding of the roles of Fe(IV) and Fe(V) in the Fe(III)-EOS-BDD system and provides an alternative for utilizing Fe(IV) and Fe(V) under near-neutral conditions.
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Diamante , Contaminantes Químicos del Agua , Boro , Compuestos Férricos , Agua , Oxidantes , Oxidación-Reducción , ElectrodosRESUMEN
Current techniques for identifying and quantifying sulfate radicals (SO4·-) in SO4·--based advanced oxidation processes (SR-AOPs) are unsatisfactory due to their low selectivity, poor reliability, and limited feasibility for real-time quantification. In this study, naproxen (NAP) was employed as a turn-on luminescent probe for real-time quantification of SO4·- in SR-AOPs. The chemiluminescence(CL) yield (ΦCL) of the reaction of NAP with SO4·- was first determined to be 1.49 × 10-5 E mol-1 with the bisulfite activation by cerium(IV) [Ce(IV)/BS] process. Then, the maximum peak concentrations of SO4·- in the Ce(IV)/BS-NAP process was quantified to be â¼10-11 M based on the derived equation. Since ΦCL of the reaction of NAP with SO4·- was much greater than that with other reactive oxidizing species (ROS), the developed CL method worked well in selective quantification of SO4·- in various SR-AOPs (e.g., the activation of peroxymonosulfate and persulfate by iron processes). Finally, the electron transfer from NAP to SO4·- was proposed to be the critical step for CL production. This work provides a novel CL method for real-time quantification of SO4·-, which facilitates the development of SR-AOPs and their application in water and wastewater treatment.
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Contaminantes Químicos del Agua , Purificación del Agua , Naproxeno , Reproducibilidad de los Resultados , Contaminantes Químicos del Agua/análisis , Purificación del Agua/métodos , Oxidación-Reducción , SulfatosRESUMEN
Pyrrhotite is ubiquitously found in natural environment and involved in diverse (bio)processes. However, the pyrrhotite-driven bioreduction of toxic selenate [Se(VI)] remains largely unknown. This study demonstrates that Se(VI) is successfully bioreduced under anaerobic condition with the participation of pyrrhotite for the first time. Completely removal of Se(VI) was achieved at initial concentration of 10 mg/L Se(VI) and 0.56 mL/min flow rate in continuous column experiment with indigenous microbial consortium and pyrrhotite. Variation in hydrochemistry and hydrodynamics affected Se(VI) removal performance. Se(VI) was reduced to insoluble Se(0) while elements in pyrrhotite were oxidized to Fe(III) and SO42-. Breakthrough study indicated that biotic activity contributed 81.4 ± 1.07% to Se(VI) transformation. Microbial community analysis suggested that chemoautotrophic genera (e.g., Thiobacillus) could realize pyrrhotite oxidation and Se(VI) reduction independently, while heterotrophic genera (e.g., Bacillus, Pseudomonas) contributed to Se(VI) detoxification by utilizing metabolic intermediates generated through Fe(II) and S(-II) oxidation, which were further verified by pure culture tests. Metagenomic and qPCR analyses indicated genes encoding enzymes for Se(VI) reduction (e.g., serA, napA and srdBAC), S oxidation (e.g., soxB) and Fe oxidation (e.g., mtrA) were upregulated. The elevated electron transporters (e.g., nicotinamide adenine dinucleotide, cytochrome c) promoted electron transfer from pyrrhotite to Se(VI). This study gains insights into Se biogeochemistry under the effect of Fe(II)-bearing minerals and provides a sustainable strategy for Se(VI) bioremediation in natural aquifer.
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Agua Subterránea , Consorcios Microbianos , Ácido Selénico , Compuestos Férricos , Oxidación-Reducción , Compuestos FerrososRESUMEN
Objective: Living kidney donors (LKDs) experience perioperative anxiety. We designed the following study to evaluate the anxiolytic effect of transcutaneous electrical acupoint stimulation (TEAS) during the perioperative period in a group of LKDs undergoing laparotomy nephrectomy. Methods: LKDs were randomly assigned to either the TEAS or control group. Participants in the TEAS group received 30min of intervention (6-15 mA, 2-100 Hz), at Yintang (EX-HN-3), bilateral Taichong (LR3) and Neiguan (PC6) one day before surgery (D0), before induction of anesthesia (D1) and one day after surgery (D2). The participants in the control group received the same placement of electrodes but without electrical stimulation. Venous blood was collected before each intervention. Anxiety levels and recovery profiles were recorded. Results: LKDs in the TEAS group had lower anxiety level than those in the control group at D1, D2 and three days after surgery (D3). The percentage differences were: 33.3%, 25.0%, and 22.2%; [95% confidence interval (CI), (-55.1%, -11.6%), (-47.4%, -2.6%), and (-42.3%, -2.2%); P = 0.005, P = 0.034, and P = 0.035; respectively]. LKDs who received TEAS had better sleep quality and short-term recovery profiles than those in the control group. The plasma levels of 5-hydroxytryptamine (5-HT) and melatonin (MT) in the TEAS group were significantly higher than those in the control group at D1 and D2 (5-HT: P = 0.001, and P < 0.001; MT: P = 0.006, and P = 0.001). At the 3-month follow up, fewer LKDs in the TEAS group had incisional pain when compared to the control group (P = 0.032). Conclusions: Perioperative TEAS decreased perioperative anxiety and facilitated postoperative recovery in the LKDs, and potential decreased the development of chronic pain. Trial Registration: Registered at ChiCTR2000029891, http://www.chictr.org.cn/listbycreater.aspx.