Chemical Oxidation Research Articles

Honey induces changes in the molecular structure and microstructure of gluten in wheat-rye sourdoughs.

Chemical oxidizers and redox enzymes have traditionally been used to enhance the quality of baked goods. However, consumers now seek natural and clean-label ingredients, avoiding those with chemical-sounding names. Honey, a natural source of glucose oxidase (GOX), represents a promising alternative to purified enzymes for baking purposes. This study aimed to evaluate the effect of honey on the molecular structure and microstructure of gluten proteins in sourdough fermented by different lactic acid bacteria (LAB) strains. Four wheat-rye (1:1) sourdoughs were prepared, each supplemented with honey and inoculated with a different LAB strain. Additionally, two uninoculated doughs, one with honey (honey dough) and the other without (control dough), were prepared under identical conditions. Electronic paramagnetic resonance spectroscopy revealed the presence of hydrogen peroxide in honey solutions, indicating its role as an active source of GOX. Raman spectroscopy showed that honey addition altered the molecular structure of gluten by increasing the proportion of random coils at the expense of α-helix structures. This change is likely attributed to the competition between honey sugars and gluten proteins for water molecules in this system. Moreover, honey led to a decrease in the free sulfhydryl content of gluten compared to the control dough, suggesting an increase in disulfide crosslinking points. These enhanced protein-protein interactions were observed in scanning electron microscopy micrographs as a coarse gluten network composed of interconnected strands and fibrils. All LAB strains exhibited optimal acidification (pH < 4.3) in honey-supplemented sourdoughs, promoting the hydrolysis of gluten proteins into smaller fragments. Overall, honey-supplemented sourdoughs showed a gradual increase in the β-sheet content while decreasing the proportion of random coils over time. This trend suggests that the polypeptide fragments interacted through interchain hydrogen bonds, leading to a more ordered structure, which likely contributes to providing dough with good baking aptitude.

Green and sustainable degradation of ofloxacin in Fe3O4/clinoptilolite electro-Fenton system under neutral condition

BackgroundIn order to overcome the drawbacks of the pH value adjustment and Fe2+addition of traditional electro-Fenton in refractory organic wastewater treatment, we set up an electro-Fence system (FCC-EF) with multiple functions of adsorption, catalysis, and green regeneration for efficient and green degradation of ofloxacin (OFLO) wastewater under neutral condition. MethodsThe Fe3O4/clinoptilolite catalyst with adsorption function was prepared by hydrothermal synthesis method, and then characterized by energy dispersive spectrometer (EDS), transmission electron microscopy (TEM) and X-ray Diffractometer (XRD). The Fe3O4/clinoptilolite's chemical composition and oxidation state was investigated by X-ray photoelectron spectros (XPS). The degradation of OFLO and the total organic carbon (TOC) were determined through HPLC and a TOC analyzer, respectively. FindingsThe results indicate that in multi-cycle operation under current density of 6 mA·cm−2 and pH = 7, FCC-EF has a 100 % removal rate for OFLO and 80.4 ± 0.2 % removal rate for TOC at 165 min, while no iron ions are detected. The internal cycling of Fe3+/Fe2+ within Fe3O4 crystals is performed in FCC-EF. The green regeneration of Fe3O4/clinoptilolite and the efficient degradation of OFLO in multi-cycle operation could be simultaneously achieved under neutral condition.

Stability and reactivity of alkylidene dihydropyridines.

Alkylidene dihydropyridines (ADHPs) are electron-rich nucleophilic intermediates that can be readily prepared by dearomatization of 4-alkylpyridines using chloroformate reagents and mild base. Their stability and reactivity can be tuned with the chloroformate reagent used as evidenced by NMR chemical shifts and oxidation potentials. ADHPs prepared with ethyl, allyl and trichloroethyl chloroformate undergo decomposition under an oxygen atmosphere at different rates (ethyl > allyl > trichloroethyl), predominantly to the corresponding 4-acylpyridine. The ADHPs derived from benzyl chloroformate are stable towards oxidation, and those derived from phenyl chloroformate hydrolyze readily.

Photocatalytic activity of polyaniline‐potassium doped nickel oxide nanocomposites: A comprehensive investigation on multifaceted properties

AbstractPolyaniline‐potassium doped nickel oxide nanocomposites (PANI/KNO) were efficiently synthesized via an in situ chemical oxidation method, meticulously confirmed by comprehensive x‐ray diffraction, Fourier transformation infrared spectroscopy, energy dispersive x‐ray spectroscopy, selected area electron diffraction, and x‐ray photoelectron spectroscopy analyses. The crystallite size and strain exhibited distinct behaviors, while field emission scanning electron microscopy revealed a blend of irregular spherical shapes and nanofibers, further confirmed by high resolution transmission electron microscopy. These composites exhibited significantly enhanced thermal stability, surpassing PANI by 1.39 times, and showcased a band gap exceeding 3 eV, along with multiple photoluminescence peaks at room temperature (RT). Moreover, their RT AC conductivity experienced a remarkable surge by 4.91 times compared to pure polyaniline. Jonscher's Power Law model and the Havriliak–Negami relaxation model are employed to elucidate the electrical properties of composite materials. The composites displayed nonDebye relaxation behavior with increased conductivity, as observed through impedance analysis, electrical modulus evaluation, and dielectric constant assessment. Additionally, evident superparamagnetic properties and multiple magnetic domains further contributed to their effectiveness. The PANI/KNO composite demonstrated photocatalytic efficiency, achieving over 90% degradation of methylene blue dye across four cycles, thus highlighting its superior photostability. Furthermore, investigations into its response to pH variations and scavenger activity underscored its immense potential for highly effective photocatalytic applications.

The Metabolism and Disposition of Brepocitinib in Humans and Characterization of the Formation Mechanism of an Aminopyridine Metabolite.

<s><s></s></s> Brepocitinib is an oral once-daily Janus kinase 1 and Tyrosine kinase 2 selective inhibitor currently in development for the treatment of several autoimmune disorders. Mass balance and metabolic profiles were determined using accelerator mass spectrometry in six healthy male participants following a single oral 60 mg dose of 14C-brepocitinib (~300 nCi). The average mass balance recovery was 96.7% {plus minus} 6.3% with the majority of dose (88.0% {plus minus} 8.0%) recovered in urine and 8.7% {plus minus} 2.1% of the dose in recovered in feces. Absorption of brepocitinib was rapid, with maximal plasma concentrations of total radioactivity and brepocitinib achieved within 0.5 hours after dosing. Circulating radioactivity consisted primarily of brepocitinib (47.8%) and metabolite M1 (37.1%) derived from hydroxylation at the C5' position of the pyrazole ring. Fractional contributions to metabolism via cytochrome P450 (CYP) enzymes were determined to be 0.77 for CYP3A4/5 and 0.14 for CYP1A2 based on phenotyping studies in HLM. However, additional clinical studies are required to understand the potential contribution of CYP1A1. Approximately 83% of the dose was eliminated as N-methylpyrazolyl oxidative metabolites, with 52.1% of the dose excreted as M1 alone. Notably, M1 was not observed as a circulating metabolite in earlier metabolic profiling of human plasma from a multiple ascending study with unlabeled brepocitinib. Mechanistic studies revealed M1 was highly unstable in human plasma and phosphate buffer, undergoing chemical oxidation leading to loss of the 5-hydroxy-1-methylpyrazole moiety and formation of aminopyrimidine cleavage product M2. Time dependent inhibition and trapping studies with M1 yielded insights into the mechanism of this unusual and unexpected instability. Significance Statement This work describes the mass balance and metabolic profile of brepocitinib in human, a JAK1/TYK2 inhibitor being developed for treatment of autoimmune diseases.

Bioinspired Water Preorganization in Confined Space for Efficient Water Oxidation Catalysis in Metallosupramolecular Ruthenium Architectures.

ConspectusNature has established a sustainable way to maintain aerobic life on earth by inventing one of the most sophisticated biological processes, namely, natural photosynthesis, which delivers us with organic matter and molecular oxygen derived from the two abundant resources sunlight and water. The thermodynamically demanding photosynthetic water splitting is catalyzed by the oxygen-evolving complex in photosystem II (OEC-PSII), which comprises a distorted tetramanganese-calcium cluster (CaMn4O5) as catalytic core. As an ubiquitous concept for fine-tuning and regulating the reactivity of the active site of metalloenzymes, the surrounding protein domain creates a sophisticated environment that promotes substrate preorganization through secondary, noncovalent interactions such as hydrogen bonding or electrostatic interactions. Based on the high-resolution X-ray structure of PSII, several water channels were identified near the active site, which are filled with extensive hydrogen-bonding networks of preorganized water molecules, connecting the OEC with the protein surface. As an integral part of the outer coordination sphere of natural metalloenzymes, these channels control the substrate and product delivery, carefully regulate the proton flow by promoting pivotal proton-coupled electron transfer processes, and simultaneously stabilize short-lived oxidized intermediates, thus highlighting the importance of an ordered water network for the remarkable efficiency of the natural OEC.Transferring this concept from nature to the engineering of artificial metal catalysts for fuel production has fostered the fascinating field of metallosupramolecular chemistry by generating defined cavities that conceptually mimic enzymatic pockets. However, the application of supramolecular approaches to generate artificial water oxidation catalysts remained scarce prior to our initial reports, since such molecular design strategies for efficient activation of substrate water molecules in confined nanoenvironments were lacking. In this Account, we describe our research efforts on combining the state-of-the art Ru(bda) catalytic framework with structurally programmed ditopic ligands to guide the water oxidation process in defined metallosupramolecular assemblies in spatial proximity. We will elucidate the governing factors that control the quality of hydrogen-bonding water networks in multinuclear cavities of varying sizes and geometries to obtain high-performance, state-of-the-art water oxidation catalysts. Pushing the boundaries of artificial catalyst design, embedding a single catalytic Ru center into a well-defined molecular pocket enabled sophisticated water preorganization in front of the active site through an encoded basic recognition site, resulting in high catalytic rates comparable to those of the natural counterpart OEC-PSII.To fully explore their potential for solar fuel devices, the suitability of our metallosupramolecular assemblies was demonstrated under (electro)chemical and photocatalytic water oxidation conditions. In addition, testing the limits of structural diversity allowed the fabrication of self-assembled linear coordination oligomers as novel photocatalytic materials and long-range ordered covalent organic framework (COF) materials as recyclable and long-term stable solid-state materials for future applications.

Recycling lithium-ion battery graphite: Synthesis of adsorbent materials for highly efficient removal of dye and metal ions from wastewater

The fate of residual graphite derived from hydrometallurgical treatment of spent Lithium-ion batteries remains uncertain. This study dwells on the aim of identifying the potentialities of recycling residual graphite for wastewater treatment. Graphite was recovered hydrometallurgically, and new adsorption materials: graphite oxide (GO) and graphene oxide (GrO) were synthesized from the residual graphite using the chemical oxidization method. Synthesized materials showed higher interlayer spacings (GO = 0.81 nm, GrO = 0.78 nm) than the commercially available similar materials. Adsorption studies revealed higher adsorption capacities for both dye (>550 mg/g in all cases) and metal ions (highest ∼93 mg/g for Ni2+ and lowest ∼68 mg/g for Zn2+). GrO showed superior results than GO due to its high surface area and porosity despite GO having more functional groups. Moreover, produced materials showed about 97 % removal of dye and about 94 % removal of contaminated metals which are higher performance than existing commercial or similar materials. These findings highlight the promising recycling capabilities of waste graphite and suggest its potential as a substitute for natural graphite.

Anaerobic biodegradation of perfluorooctane sulfonate (PFOS) and microbial community composition in soil amended with a dechlorinating culture and chlorinated solvents

Perfluorooctane sulfonate (PFOS), one of the most frequently detected per- and polyfluoroalkyl substances (PFAS) occurring in soil, surface water, and groundwater near sites contaminated with aqueous film-forming foam (AFFF), has proven to be recalcitrant to many destructive remedies, including chemical oxidation. We investigated the potential to utilize microbially mediated reduction (bioreduction) to degrade PFOS and other PFAS through addition of a known dehalogenating culture, WBC-2, to soil obtained from an AFFF-contaminated site. A substantial decrease in total mass of PFOS (soil and water) was observed in microcosms amended with WBC-2 and chlorinated volatile organic compound (cVOC) co-contaminants — 46.4 ± 11.0 % removal of PFOS over the 45-day experiment. In contrast, perfluorooctanoate (PFOA) and 6:2 fluorotelomer sulfonate (6:2 FTS) concentrations did not decrease in the same microcosms. The low or non-detectable concentrations of potential metabolites in full PFAS analyses, including after application of the total oxidizable precursor assay, indicated that defluorination occurred to non-fluorinated compounds or ultrashort-chain PFAS. Nevertheless, additional research on the metabolites and degradation pathways is needed. Population abundances of known dehalorespirers did not change with PFOS removal during the experiment, making their association with PFOS removal unclear. An increased abundance of sulfate reducers in the genus Desulfosporosinus (Firmicutes) and Sulfurospirillum (Campilobacterota) was observed with PFOS removal, most likely linked to initiation of biodegradation by desulfonation. These results have important implications for development of in situ bioremediation methods for PFAS and advancing knowledge of natural attenuation processes.

Bacteria in clouds biodegrade atmospheric formic and acetic acids

Abstract. Formic and acetic acids are major organic species in cloud water and affect precipitation acidity. In atmospheric models, their losses are limited to chemical oxidation in the gas and aqueous phases and deposition processes. Previous lab studies suggest that these acids can be efficiently biodegraded in water by atmospherically relevant bacteria. However, the importance of biodegradation as a loss process in the atmospheric multiphase system has not been fully assessed. We implemented biodegradation as a sink of formic and acetic acids in a detailed atmospheric multiphase chemistry model. In our model, biodegradation is considered in 0.1 % of cloud droplets according to atmospheric bacteria concentrations of 0.1 cm−3. We predict that up to 20 ppt h−1 formic acid and 5 ppt h−1 acetic acid are biodegraded. This translates into a concentration change of 20 % and 3 % in addition to that caused by chemical losses. Our sensitivity studies suggest that acetic acid is most efficiently biodegraded at pH &gt; 5, whereas biodegradation is least efficient for formic acid under such conditions. This trend can be explained by the fact that formic acid partitions more efficiently into the aqueous phase due to its higher Henry's law constant (KH,eff(HCOOH)=2×105 M atm−1 vs. KH,eff(CH3COOH)=3×104 M atm−1 at pH = 5). Therefore, under such conditions, formic acid evaporates less efficiently from bacteria-free droplets, resulting in less formic acid in the gas phase for dissolution bacteria-containing droplets to replenish biodegraded acid. Our analysis demonstrates that previous estimates of the importance of atmospheric biodegradation were often biased high as they did not correctly account for such uptake limitation in bacteria-containing droplets. The results suggest that, under specific conditions, biological processes can significantly affect atmospheric composition and concentrations in particular volatile, moderately soluble organics.

Understanding the dynamics of enhanced light non-aqueous phase liquids (LNAPL) remediation at a polluted site: Insights from hydrogeophysical findings and chemical evidence

This study intricately unfolds a pioneering methodology for remediating contaminants in a persistent light non-aqueous phase liquids (LNAPL)-contaminated site. The remediation strategy seamlessly integrates enhanced desorption and in-situ chemical oxidation (ISCO), orchestrating the injection of PetroCleanze® (a desorbent) and RegenOx® (an oxidizer) through meticulously designed wells. These injections, based on detailed geological and hydrogeological assessments, aim at mobilizing residual contaminants for subsequent extraction. Real-time subsurface dynamics are investigated through geophysical monitoring, employing electrical resistivity tomography (ERT) to trace reagent migration pathways via their effect on bulk electrical conductivity. The integration of groundwater sampling data aims at providing additional insights into the transformations of contaminants in the spatiotemporal context. Vivid two-dimensional time-lapse ERT sections showcase the evolution of resistivity anomalies, providing high-resolution evidence of the heterogeneity, dispersion pathways of desorbent and oxidant, and residual LNAPL mobilization. Hydrochemical analyses complement this, revealing effective mobilization processes with increasing aqueous concentrations of total petroleum hydrocarbons (TPH) over time. Speciation analysis unveils the intricate interplay of desorption and oxidation, portraying the dynamic fractionation of hydrocarbon components. The hydrogeophysical and data-driven framework not only delivers qualitative and quantitative insights into reagent and contaminant distribution but also enhances understanding of spatial and temporal physio-chemical changes during the remediation process. Time-lapse ERT visually narrates the reagent's journey through time, while chemical analyses depict the unfolding processes of desorption and oxidation across space and time. The coupling of hydrogeophysical and chemical findings pictures the transformations of pollutants following the sequence of product injection and the push and pull activities, capturing the removal of mobilized contaminants through hydraulic barrier wells. This enhanced understanding proves instrumental towards optimizing and tailoring remediation efforts, especially in heterogeneous environmental settings. This study establishes a new standard for a sophisticated and innovative contaminant remediation approach, advancing environmental practices through the harmonized analysis of geophysical and chemical data.

Interactions between methyl octabromo ether flame retardant and expanded polystyrene microplastics in the photoaging process

Expanded polystyrene (EPS) plastic is widely used because of its low density and lightweight properties, enabling it to float on water and increase its exposure to sunlight. In this study, we simulated the photoaging process of flame retardant-added EPS (FR-EPS) and common original EPS (OR-EPS) microplastic (MP) particles with and without methyl octabromoether flame retardant (MOBE) in the laboratory to explore the effect of MOBE on the photodegradation of EPS. Results showed that MOBE accelerated size reduction and surface hole formation on the particles, hastening the shedding and replacement of particle surfaces. FR-EPS particles exhibited a weight loss exceeding that of OR-EPS, reaching 40.85 ± 3.72% after 36 days of irradiation. Moreover, rapid physical peeling of the FR-EPS surface was accompanied by continuous chemical oxidation and fluctuations of the carbonyl index and O/C ratio. A diffusion model based on Fick's second law fitted well for the concentration of MOBE remaining in FR-EPS particles. MOBE's sensitivity to direct photochemical reactions inhibited the early-stage photoaging of EPS MP particles by competing for photons. However, MOBE as chromophores could absorb photons and produce •OH to promote the aging of EPS. Moreover, the capacity of EPS to absorb light energy also accelerated MOBE degradation. These findings suggested that the photoaging behavior of commercial EPS products containing flame retardants in the environment is quite different from that of pure EPS, indicating that additive-plastic interactions significantly alter MP fate and environmental risks.

Hierarchical sintered porous surfaces with enhanced pool boiling heat transfer performance for high-power cooling applications

Porous surfaces fabricated by sintering maintain good pool boiling heat transfer performances and have the advantages of high processing efficiency and low cost. Hierarchical sintered porous structures (HS) composed of copper mesh and porous column array are fabricated by a sintering process. Chemical oxidation and high-temperature reduction are used to deposit micro/nano coating on HS (NHS). The porous column array induces the capillary value effect and enhances the capillary performances of HS and NHS. The micro/nano coating provides more nucleation sites and further enhances the capillary velocity. The faster capillary velocity and higher volumetric flow rate of HS and NHS result in much higher critical heat flux (CHF) than sintered mesh surfaces (MS). The CHF of NHS reaches 2422.9 kW/m2, which is 43.7 % and 21 % higher than that of MS and HS, respectively. A good linear relationship between the volumetric flow rate and the CHF is observed. Besides, the porous structures greatly enhance the heat transfer coefficient (HTC). The micro/nano coating of NHS has a more obvious enhancement effect on HTC at low heat fluxes. The pool boiling heat transfer performance of HS and NHS is comparable to or even better than those in literature and has the feasibility of application in high-power cooling scenarios.

Dual-step Redox Engineering of Two-Dimensional CoNi-Alloy Embedded B, N-Doped Carbon Layers towards Tunable Electromagnetic Wave Absorption and Light-Weight Infrared Stealth Heat Insulation Devices.

Two-dimensional layered metallic graphite composites as promising electromagnetic wave absorption materials (EWAMs) for their combined properties of abundant interlayer free spaces, rich metallic polarized sites and high conductivity, but the controllable synthesis remains rather challenging. Herein, a dual-step Redox engineering strategy was developed by employing cobalt boron imidazolate framework (Co-BIF) to construct a two-dimensional CoNi-alloy embedded B, N-doped carbon layers (2D-CNC), as a promising EWAM. In the first step, a chemical etching oxidation process on Co-BIF was used to obtain an optimized 2D-CoNi-layered double hydroxide (2D-CoNi-LDH) intermediate and in the second, high-temperature calcination reduction was implemented to modify graphitization the degree of the 2D-CNC. The obtained sample delivers superior reflection loss (RLmin) of -60.1dB and wide effective absorption bandwidth (EAB) of 6.24GHz. The synergy mechanisms of interfacial/dipole polarization and magnetic coupling were in-depth evidenced by the hologram and Lorentz electron microscopy, revealing its significant contribution on multireflection and impedance matching. Further theoretical evaluation by COMSOL simulation in different fields based on the dynamic loss process towards the test ring reveals the in situ EW attenuation process. This work presents a strategy to develop multifunctional light-weight infrared stealthy aerogel with superior pressure-resistant, anti-corrosion and heat-insulating properties for future applications. This article is protected by copyright. All rights reserved.

Self-discharge in flowless Zn-Br2 batteries and its mitigation

Several decades after the invention of the flow Zn-Br2 systems persistent attempts have been made to develop stationary Zn-Br2 batteries. Such development should increase the energy density of the system simultaneously significantly reducing their cost and opening new challenges associated with the cell design and its performance. One of the major concerns is the rapid self-discharge of stationary systems leading to spontaneous charge loss during battery storage time. While self-discharge in flow cells is generally attributed to the chemical oxidation of the Zn anode, we show that the origin of self-discharge in a static configuration is completely different. By systematic investigations of activated carbon with different surface areas under varied charging conditions, mechanistic insights into this phenomenon were provided. Based on this understanding, we proposed herein an effective way to suppress the cathode's self-discharge by encapsulation of a bromine complexing agent inside the electrode's pore matrix. The modified electrodes unveil unique chemical kinetics of deaggregation of the stable fuse salt phase composed of bromine complexing agent and Br3− anions upon discharging. To the best of our knowledge, such a phenomenon has not been reported yet. The proposed system demonstrates high capacity (up to 300mAh/g) and impressive long-term stability.

Oxidation of chromium(Ⅲ): A potential risk of using chemical oxidation processes for the remediation of 2-chlorophenol contaminated soils

Chemical oxidation processes are widely used for the remediation of organically contaminated soils, but their potential impact on variable-valence and toxic metals such as chromium (Cr) is often overlooked. In this study, we investigated the risk of Cr(Ⅲ) oxidation in soils during the remediation of 2-chlorophenol (2-CP) contaminated soils using four different processes: Potassium permanganate (KMnO4), Modified Fenton (Fe2+/H2O2), Alkali-activated persulfate (S2O82-/OH-), and Fe2+-activated persulfate (S2O82-/Fe2+). Our results indicated that the KMnO4, Fe2+/H2O2, and S2O82-/Fe2+ processes progressively oxidized Cr(III) to Cr(Ⅵ) during the 2-CP degradation. The KMnO4 process likely involved direct electron transfer, while the Fe2+/H2O2 and S2O82-/Fe2+ processes primarily relied on HO• and/or SO4•- for the Cr(III) oxidation. Notably, after 4 h of 2-CP degradation, the Cr(VI) content in the KMnO4 process surpassed China's 3.0 mg·kg-1 risk screening threshold for Class I construction sites, and further exceeded the 5.7 mg·kg-1 limit for Class II construction sites after 8 h. Conversely, the S2O82-/OH- process exhibited negligible oxidation of Cr(III), maintaining a low oxidation ratio of 0.13%, as highly alkaline conditions induced Cr(III) precipitation, reducing its exposure to free radicals. Cr(III) oxidation ratio was directly proportional to oxidant dosage, whereas the Fe2+/H2O2 process showed a different trend, influenced by the concentration of reductants. This study provides insights into the selection and optimization of chemical oxidation processes for soil remediation, emphasizing the imperative for thorough risk evaluation of Cr(III) oxidation before their application.

Harnessing bromide ions to boost peroxymonosulfate for Reactive Yellow 145 dye degradation

Bromide (Br−) was found in the fresh waters at concentrations from 0.1 to 1 mg/L and can be used to activate peroxymonosulfate (PMS) as a widely used chemical oxidation agent. In the present study, the reaction between PMS and Br− ions (PMS/Br− process) for the effective degradation of reactive yellow 145 (RY-145) dye was investigated by changing operational parameters vis solution pH, dosage of Br− ions and PMS, RY-145 concentration, and reaction time. Based on the results, the simultaneous presence of PMS and Br− ions in the solution led to efficient degradation of RY-145 with a synergistic index of 11.89. The degradation efficiency of RY-145 was decreased in severe basic pH and the presence of CO32− ions as a coexisting anion. Likewise, 4 mg/L of humic acid (HA), used as a classic scavenger, led to a 26.53% decrease in the RY-145 degradation efficiency. The free bromine (HOBr/OBr−), superoxide radical (●O2–), and singlet oxygen (1O2) was the dominant oxidation agents in RY-145 degradation, which confirmed the nonradical degradation pathway. In addition, PMS/Br− process showed excellent ability in mineralizing RY-145 in different aqueous solutions (total organic carbon (TOC) decreased 86.39% in deionized water and 78.23% in tap water). Although pollutants such as azo dyes can be effectively removed in the PMS/Br− process, the formation of byproducts should be strategically controlled and special attention should be paid when the PMS-based advance oxidation process is applied to treat Br− containing solutions.

Ultrasound, Hydrogen Peroxide, and Persulfate in Hybrid Advanced Oxidation Processes(AOPs): A Comparative Study for the Reuse of Sewage Treatment Effluent

Objectives : As the variety and quantity of recalcitrant pollutants such as pharmaceuticals, pesticides, endocrine disruptors, and cosmetic products discharged into water bodies steadily increase, the need for AOPs following biological wastewater treatment processes is growing. In this study, we compared the Total Organic Carbon (TOC) removal capabilities of conventional AOPs, ultrasound, hydrogen peroxide, and persulfate-based multiple AOPs on the final effluent of S wastewater treatment plant. The study also evaluated the feasibility of wastewater reuse by examining the optimal operating conditions of the applied AOPs.Methods : The removal characteristics of TOC were investigated based on reaction time, US frequency, and oxidant dosage for the following conditions: ultrasound (US) alone, individual treatments with hydrogen peroxide (H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt;) and persulfate (PS) as oxidants, combined US/H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt; and US/PS dual AOPs, and a US/PS/H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt; multi-AOPs system.Results and Discussion : Only US oxidation treatment at 80 kHz for 60 minutes resulted in a 14.4% TOC removal efficiency. Individual treatment with H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt; at 174 mM showed 69.2% removal efficiency, while persulfate oxidation treatment at 43.5 mM showed 13.8%. The PS/H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt; oxidation treatment showed 68.5% removal efficiency at 174 mM H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt; and 0.52 mM PS, and an 85.3% removal efficiency at 2.08 mM PS and 350 mM H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt; conditions. Under the same 80 kHz ultrasound conditions, the combined US and other oxidant treatment resulted in an increased TOC removal efficiency: 87.8% for US/H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt; at 174 mM H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt;, and 81.9% for US/PS at 43.5 mM PS. Additionally, the multi-treatment with US, PS, and H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt; showed a removal efficiency of 87.0% at 2.08 mM PS and 350 mM H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt;, and 91.1% at 174 mM H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt; and 0.52 mM PS conditions.Conclusion : In this study, among the AOPs, the oxidation treatment with US/PS/H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt; exhibited the highest TOC removal efficiency at 91.1%. The integration of chemical oxidants with US demonstrated significant improvement in TOC removal capabilities, with PS showing superior performance at the same concentration conditions among the utilized chemical oxidants in the multi-AOPs. Although H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt; also displayed commendable TOC removal abilities, its oxidation efficiency was lower at low concentration injections, whereas higher concentrations of H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt; injections proved to be more effective in oxidation.

Environmental Markers of Plastics and Microplastics.

The slow reaction rates to chemical and photochemical degradation are well-known properties of plastics. However, large plastic surfaces exposed to environmental conditions release particles and compounds that affect ecosystems and human health. The aim of this work was to identify compounds associated with the degradation of polyethylene (PE), polystyrene (PS), and polyvinyl chloride (PVC) microplastics (markers) on silica and sand and evaluate their use to screen microplastics on natural sand. Products were identified by using targeted and untargeted LC-HRMS analysis. All polymers underwent chemical oxidation on silica. PE released dicarboxylic acids (HO2C-(CH2)n-CO2H (n = 4-30), while PS released cis/trans-chalcone, trans-dypnone, 3-phenylpropiophenone, and dibenzoylmethane. PVC released dicarboxylic acids and aromatic compounds. Upon irradiation, PE was stable while PS released the same compounds as under chemical oxidation but at lower yields. Under the above condition, PVC generated HO2C-[CH2-CHCl]n-CH2-CO2H and HO2C-[CH2-CHCl]n-CO2H (n = 2-19) dicarboxylic acids. The same products were detected on sand but at a lower concentration than on silica due to better retention within the pores. Detection of markers of PE and PS on natural sand allowed us to screen microplastics by following a targeted analysis. Markers of PVC were not detected before or after thermal/photo-oxidation due to the low release of compounds and limitations associated with surface exposure/penetration of radiation.

WLI, XPS and SEM/FIB/EDS Surface Characterization of an Electrically Fluted Bearing Raceway

Electrical bearing currents may disturb the performance of the bearings via electro-corrosion if they surpass a limit of ca. 0.1 to 0.3 A/mm2. A continuous current flow, or, after a longer time span, an alternating current or a repeating impulse-like current, damages the raceway surface, leading in many cases to a fluting pattern on the raceway. Increased bearing vibration, audible noise, and decreased bearing lubrication as a result may demand a replacement of the bearings. Here, an electrically corroded axial ball bearing (type 51208) with fluting patterns is investigated. The bearing was lubricated with grease lubrication and was exposed to 4 A DC current flow. It is shown that the electric current flow causes higher concentrations of iron oxides and iron carbides on the bearing raceway surface together with increased surface roughness, leading to a mixed lubrication also at elevated bearing speeds up to 1500 rpm. The “electrically insulating” iron oxide layer and the “mechanically hard” iron carbide layer on the bearing steel are analysed by WLI, XPS, SEM, and EDS. White Light Interferometry (WLI) is used to provide an accurate measurement of the surface topography and roughness. X-ray Photoelectron Spectroscopy (XPS) measurements are conducted to analyze the chemical surface composition and oxidation states. Scanning Electron Microscopy (SEM) is applied for high-resolution imaging of the surface morphology, while the Focused Ion Beam (FIB) is used to cut a trench into the bearing surface to inspect the surface layers. With the Energy Dispersive X-ray spectrometry (EDS), the presence of composing elements is identified, determining their relative concentrations. The electrically-caused iron oxide and iron carbide may develop periodically along the raceway due to the perpendicular vibrations of the rolling ball on the raceway, leading gradually to the fluting pattern. Still, a simulation of this vibration-induced fluting-generation process from the start with the first surface craters—of the molten local contact spots—to the final fluting pattern is missing.

Protecting against micropollutants in water storage tanks using in-situ TiO2 coated quartz optical fibers

Photocatalyst-coated optical fibers (P-OFs) using UV-A LEDs offer a highly promising solution for the degradation of micropollutants within municipal, reuse, industrial or home distribution systems, by integrating P-OFs into water storage tanks. P-OFs have photocatalysts attached to bundles of optical fibers, enabling their direct deployment within tanks. This eliminates the necessity for photocatalyst slurries, which would require additional membrane or separation systems. However, a current limitation of P-OFs is light management, specifically light oversaturation of the coated photocatalysts and short light transmission distances along fibers. This study overcomes this limitation and reveals strategies to improve the light dissipation uniformity along P-OFs, and demonstrates the performance of P-OFs on degrading a model micropollutant, carbamazepine (CBZ). Key tunable variables of fibers and light emission conditions, including photocatalyst coating patchiness (p), minimum light incident angles (θm), radiant flux launched to fibers (Φi), and fiber diameters (D), were modeled to establish their relationships with the light dissipation uniformity in TiO2-coated quartz optical fibers (TiO2-QOFs). We then validated modeling insights by conducting experiments to examine how these variables influence the generation of evanescent waves which are localized energy on fiber surfaces, leading to either photocatalyst activation or the recapture of unused light back into fibers. We observed substantial enhancements in evanescent waves generation by decreasing p and increasing θm, resulting in uniform light dissipation which reduces light oversaturation and improves light transmission distances. Moreover, these optimizations led to a remarkable three-fold improvement in CBZ degradation rates and a 65% reduction in energy consumption. Such improvement substantially reduces the capital and operational cost and enhances practicality of energy-efficient photocatalysis without additional chemical oxidants for micropollutant degradation in water storage tanks.