Electronic structure modulation of iron sites with fluorine coordination enables ultra-effective H2O2 activation.

Electronic structure modulation of active sites is critical important in Fenton catalysis as it offers a promising strategy for boosting H2O2 activation. However, efficient generation of hydroxyl radicals (•OH) is often limited to the unoptimized coordination environment of active sites. Herein, we report the rational design and synthesis of iron oxyfluoride (FeOF), whose iron sites strongly coordinate with the most electronegative fluorine atoms in a characteristic moiety of F-(Fe(III)O3)-F, for effective H2O2 activation with potent •OH generation. Results demonstrate that the fluorine coordination plays a pivotal role in lowering the local electron density and optimizing the electronic structures of iron sites, thus facilitating the rate-limiting H2O2 adsorption and subsequent peroxyl bond cleavage reactions. Consequently, FeOF exhibits a significant and pH-adaptive •OH yield (~450 µM) with high selectivity, which is 1 ~ 3 orders of magnitude higher than the state-of-the-art iron-based catalysts, leading to excellent degradation activities against various organic pollutants at neutral condition. This work provides fundamental insights into the function of fluorine coordination in boosting Fenton catalysis at atomic level, which may inspire the design of efficient active sites for sustainable environmental remediation.

BézierCE: Low-Light Image Enhancement via Zero-Reference Bézier Curve Estimation.

Due to problems such as the shooting light, viewing angle, and camera equipment, low-light images with low contrast, color distortion, high noise, and unclear details can be seen regularly in real scenes. These low-light images will not only affect our observation but will also greatly affect the performance of computer vision processing algorithms. Low-light image enhancement technology can help to improve the quality of images and make them more applicable to fields such as computer vision, machine learning, and artificial intelligence. In this paper, we propose a novel method to enhance images through Bézier curve estimation. We estimate the pixel-level Bézier curve by training a deep neural network (BCE-Net) to adjust the dynamic range of a given image. Based on the good properties of the Bézier curve, in that it is smooth, continuous, and differentiable everywhere, low-light image enhancement through Bézier curve mapping is effective. The advantages of BCE-Net's brevity and zero-reference make it generalizable to other low-light conditions. Extensive experiments show that our method outperforms existing methods both qualitatively and quantitatively.

Target-prepared sludge biochar-derived synergistic Mn and N/O induces high-performance periodate activation for reactive iodine radicals generation towards ofloxacin degradation.

Converting waste activated sludge into catalysts for the removal of antibiotics in water fulfils the dual purpose of waste-to-resource and hazardous pollution elimination. In this study, sludge-derived biochar (SDB) for efficient periodate (PI) activation was first prepared via one-step pyrolysis of potassium permanganate-polyhexamethylenebiguanide conditioned sludge without additional modification. The SDB (750 °C)-PI system degraded 100% ofloxacin (OFL, 41.5 µM) within 6 min and was almost undisturbed by inorganic ions or humic acids. The experimental results confirmed that the predominant role of reactive iodine species (RIS) and the auxiliary involvement of singlet oxygen (1O2) jointly contributed to the OFL degradation. Theoretical calculations further indicated that the synergy between Mn and N/O induced local charge redistribution and improved electron transfer capability of SDB, leading to the formation of electron-rich Mn sites and enhanced Mn(II)↔Mn(III)↔Mn(IV) redox to promote PI activation. More importantly, the enhanced adsorption and charge transfer of PI on the Mn site of the Mn-N/O-C structures induced the I-O bond stretching and the rapid generation of RIS. This study offered a cost-effective strategy for developing SDB-based catalysts, further advancing the comprehension of sludge management and the intricate mechanisms underlying RIS formation in PI-advanced oxidation processes.

Sex-Based Differences in the Presentation and Outcomes of Acute Pulmonary Embolism: A Systematic Review and Meta-Analysis.

BACKGROUND: The study aimed to review differences in the presentation and outcomes of acute pulmonary embolism (PE) between men and women. METHODS: PubMed, CENTRAL, Web of Science, and Embase were searched for studies comparing clinical features or outcomes of PE between men and women. Baseline comorbidities, risk factors, clinical features, and mortality rates were also compared between men and women. RESULTS: Fourteen studies were included. It was noted that men presented with PE at a statistically significantly younger age than women (P < .001). Smoking history (P < .001), lung disease (P = .004), malignancy (P = .02), and unprovoked PE (P = .004) were significantly more frequent among men than among women. There was no difference between the sexes for hypertension, diabetes, and a history of recent immobilization. A significantly higher proportion of men presented with chest pain (P = .02) and hemoptysis (P < .001), whereas syncope (P = .005) was more frequent in women. Compared with men, women had a higher proportion of high-risk PE (P = .003). There was no difference in the use of thrombolytic therapy or inferior vena cava filter. Neither crude nor adjusted mortality rates were significantly different between men and women. CONCLUSION: This review found that the age at presentation, comorbidities, and symptoms of PE differed between men and women. Limited data also suggest that women more frequently had high-risk PE compared with men, but the use of thrombolytic therapy did not differ between the 2 sexes. Importantly, both crude and adjusted data show that the mortality rate did not differ between men and women.

Unveiling the occurrence, distribution, removal, and environmental impacts of 65 emerging contaminants in neglected fresh leachate from municipal solid waste incineration plants.

Emerging contaminants (ECs) are commonly found in environmental media. Yet leachate from municipal solid waste incineration plants (MSWIPs), which can serve as a reservoir for various contaminants, including ECs, has received little investigation. To address this gap, 65 ECs were analyzed in the fresh leachate and biological effluent from three major MSWIPs in Shanghai. Results indicated that over half (56%) of the 65 ECs were detected in fresh leachate. Different ECs would be removed to varying degrees after biological treatment, including polycyclic aromatic hydrocarbons (PAHs) (65%), polybrominated diphenyl ethers (PBDEs) (51%), phthalate esters (PAEs) (36%), and organophosphorus pesticides (OPPs) (34%). Notably, for tetrabromobisphenol A (TBBPA), a PBDE substitute, only 2% was removed after biological treatment, while polychlorinated biphenyls (PCBs) were effectively removed at 83%. Water solubility and the octanol-water partition coefficient are key factors influencing the distribution and removal of ECs in leachate. the effluent will still contain refractory ECs even after the biological treatment. These residual ECs discharged to sewers can impact wastewater treatment plants or contaminate surface water and groundwater. These findings provide insights into the leachate contamination by ECs, their environmental fate, factors affecting their behavior, and potential environmental impacts.

Antiviral drugs in wastewater are on the rise as emerging contaminants: A comprehensive review of spatiotemporal characteristics, removal technologies and environmental risks.

Antiviral drugs (ATVs) are widely used to treat illnesses caused by viruses. Particularly, ATVs were consumed in such large quantities during the pandemic that high concentrations were detected in wastewater and aquatic environment. Since ATVs are not fully absorbed by the human or animal body, this results in large amounts of them being discharged into the sewage through urine or feces. Most ATVs can be degraded by microbes at wastewater treatment plants (WWTPs), while some ATVs either require deep treatment to reduce concentration and toxicity. Parent and metabolites residing in effluent posed a varying degree of risk when entering the aquatic environment, while increasing the potential of natural reservoirs for environmentally acquired antiviral drug resistance potential. There is a rising research on the behavior of ATVs in the environment has surged since the pandemic. In the context of multiple viral diseases worldwide, especially during the current COVID-19 pandemic, a comprehensive assessment of the occurrence, removal, and risk of ATVs is urgently needed. This review aims to discuss the fate of ATVs in WWTPs from various regions in the world with wastewater as the main analyzing object. The ultimate goal is to focus on ATVs with high ecological impact and regulate their use or develop advanced treatment technologies to mitigate the risk to the environment.

SR-FEINR: Continuous Remote Sensing Image Super-Resolution Using Feature-Enhanced Implicit Neural Representation.

Remote sensing images often have limited resolution, which can hinder their effectiveness in various applications. Super-resolution techniques can enhance the resolution of remote sensing images, and arbitrary resolution super-resolution techniques provide additional flexibility in choosing appropriate image resolutions for different tasks. However, for subsequent processing, such as detection and classification, the resolution of the input image may vary greatly for different methods. In this paper, we propose a method for continuous remote sensing image super-resolution using feature-enhanced implicit neural representation (SR-FEINR). Continuous remote sensing image super-resolution means users can scale a low-resolution image into an image with arbitrary resolution. Our algorithm is composed of three main components: a low-resolution image feature extraction module, a positional encoding module, and a feature-enhanced multi-layer perceptron module. We are the first to apply implicit neural representation in a continuous remote sensing image super-resolution task. Through extensive experiments on two popular remote sensing image datasets, we have shown that our SR-FEINR outperforms the state-of-the-art algorithms in terms of accuracy. Our algorithm showed an average improvement of 0.05 dB over the existing method on ×30 across three datasets.

Drift of sparse and dense spiral waves under joint external forces.

Many methods have been employed to investigate the drift behaviors of spiral waves in an effort to understand and control their dynamics. Drift behaviors of sparse and dense spirals induced by external forces have been investigated, yet they remain incompletely understood. Here we employ joint external forces to study and control the drift dynamics. First, sparse and dense spiral waves are synchronized by the suitable external current. Then, under another weak current or heterogeneity, the synchronized spirals undergo a directional drift, and the dependence of their drift velocity on the strength and frequency of the joint external force is studied.

Dissolution behaviors of a visible-light-responsive photocatalyst BiVO4: Measurements and chemical equilibrium modeling.

Despite of the extensive research in semiconductor photocatalysis with respect to material and device innovations, much of the fundamental aquatic chemistry of those new materials that governs their environmental hazard and implications remains poorly understood. BiVO4 has long been recognized as a promising visible-light-responsive photocatalyst. However, the solubility product (Ksp) of BiVO4 and the mechanistic understanding of the non-stoichiometric dissolution of BiVO4 remain unclear. Here, we investigated the solubility of BiVO4 via the observation on its non-stoichiometric dissolution in the pH range of 4-9. Combining dissolution experiments, adsorption behavior and thermodynamic equilibrium calculations, the Ksp of BiVO4 was determined to be 10-35.81±0.51. The solubility and stability of BiVO4 were strongly pH-dependent, with the lowest solubility and highest stability near pH 5. Furthermore, we tested the effect of illumination on the dissolution of BiVO4, which was significantly enhanced by light. Under both dark and illumination conditions, adsorption of dissolved bismuth by BiVO4 solids was the main reason for the non-stoichiometric dissolution of BiVO4, and could be modeled by including an additional surface complexation reaction. Thus, the results highlighted the importance of considering the dissolution of photocatalysts, and presented a feasible method to evaluate environmental stability and risks of other semiconductor materials.

Medium-Low Temperature Conditions Induce the Formation of Environmentally Persistent Free Radicals in Microplastics with Conjugated Aromatic-Ring Structures during Sewage Sludge Pyrolysis.

Medium-low temperature pyrolysis is an effective method of retaining active components in sludge char. However, we found that incomplete cracking reactions resulted in residues of microplastics (MPs) remaining in the char; moreover, high levels of environmentally persistent free radicals (EPFRs) were detected in these MPs. Here, we investigated the temperature-dependent variations in the char-volatile products derived from sludge and MPs under different pyrolysis scenarios using multiple in situ probe coupling techniques and electron paramagnetic resonance spectroscopy, thereby identifying the sources of EPFRs and elucidating the corresponding formation-conversion mechanisms. The temperature was the key factor in the formation of EPFRs; in particular, in the 350-450 °C range, the abundance of EPFRs increased exponentially. Reactive EPFR readily formed in MPs with conjugated aromatic-ring structures (polyethylene terephthalate and polystyrene) at a temperature above 350 °C; EPFR concentrations were 5-17 times higher than those found in other types of polymers, and these radicals exhibited half-lives of more than 90 days. The EPFR formation mechanism could be summarized as solid-solid/solid-gas interfacial interactions between the polymers and the intermediate products from sludge pyrolysis (at 160-350 °C) and the homolytic cleavage-proton transfer occurring in the polymers themselves under the dual action of thermal induction and acid sites (at 350-450 °C). Based on the understanding of the evolution of EPFRs, temperature regulation and sludge components conditioning may be effective approaches to inhibit the formation of EPFRs in MPs, constituting reliable strategies to diminish the environmental risk associated with the byproducts of sludge pyrolysis.

Electrochemical pretreatment enhancing co-fermentation of waste activated sludge and food waste into volatile fatty acids: Performance, microbial community dynamics and metabolism.

Waste activated sludge (WAS) has low biodegradability that restricts acidogenic fermentation (AF), thereby limiting the high-value volatile fatty acids (VFAs) production. This study investigated an alternative electrochemical pretreatment (EPT) approach that can facilitate AF of WAS and food waste (FW) and therefore enhance VFAs production. The results showed through introducing 50 % volatile solid basis of FW (containing massive chloride) into WAS, a 60-min EPT produced reactive chlorine species (RCS), which diffused into WAS-FW inner layers resulting in cell lysis, therefore significantly promoted and accelerated WAS-FW disintegration, contributing to more soluble and biodegradable dissolved organic matter (DOM). Then during the subsequent 15-day acidogenic co-fermentation (Co-AF), the residual RCS (approximate 5 mg Cl2/L) also caused acidogenic bacteria (including Prevotella_7, Lactobacillus and Veillonella) gradually outcompeted methanogens due to their different tolerance to residual RCS. Consequently, the maximum VFAs yield of the WAS-FW Co-AF with EPT was 40.8 % higher than WAS-AF without EPT.

Low-Light Image Enhancement via Retinex-Style Decomposition of Denoised Deep Image Prior.

Low-light images are a common phenomenon when taking photos in low-light environments with inappropriate camera equipment, leading to shortcomings such as low contrast, color distortion, uneven brightness, and high loss of detail. These shortcomings are not only subjectively annoying but also affect the performance of many computer vision systems. Enhanced low-light images can be better applied to image recognition, object detection and image segmentation. This paper proposes a novel RetinexDIP method to enhance images. Noise is considered as a factor in image decomposition using deep learning generative strategies. The involvement of noise makes the image more real, weakens the coupling relationship between the three components, avoids overfitting, and improves generalization. Extensive experiments demonstrate that our method outperforms existing methods qualitatively and quantitatively.

Radix Astragali residue-derived porous amino-laced double-network hydrogel for efficient Pb(II) removal: Performance and modeling.

Valorizing solid waste for heavy metal adsorption is highly desirable to avoid global natural resources depletion. In this study, we developed a new protocol to valorize Radix Astragali residue (one of the Chinese medicine residues) into a low-cost, chemically robust, and highly permeable (ca. 90%) amino-laced porous double-network hydrogel (NH2-CNFs/PAA) for efficient Pb(II) adsorption. The NH2-CNFs/PAA showed (i) excellent Pb(II) adsorption capacity (i.e., 994.5 mg g-1, ~4.8 mmol g-1), (ii) fast adsorption kinetics (kf = 2.01 ×10-5 m s-1), (iii) broad working pH range (2.0-6.0), and (iv) excellent regeneration capability (~15 cycles). (v) excellent performance in various real water matrices on Pb(II) removal. Moreover, its high selectivity (distribution coefficient Kd ~2.4 ×106 mL g-1) toward Pb(II) was owing to the present of abundant amino groups (-NH2). Furthermore, the fix-bed column test indicated the NH2-CNFs/PAA can effectively remove 114.6 bed volumes (influent concentration ~5000 µg L-1) with an enrichment factor 10.9. The full-scale system modeling (i.e., pore surface diffusion model (PSDM)) has been applied to predict the NH2-CNFs/PAA performance on Pb(II) removal. Overall, we have provided an alternative "win-win" scenario that can resolve the Chinese medicine residues disposal issue by valorizing it into high performance gel-based adsorbents for efficient heavy metal removal.

A sustainable reuse strategy of converting waste activated sludge into biochar for contaminants removal from water: Modifications, applications and perspectives.

Conversion of sewage sludge to biochar for contaminants removal from water achieves the dual purpose of solid waste reuse and pollution elimination, in line with the concept of circular economy and carbon neutrality. However, the current understanding of sludge-derived biochar (SDB) for wastewater treatment is still limited, with a lack of summary regarding the effect of modification on the mechanism of SDB adsorption/catalytic removal aqueous contaminants. To advance knowledge in this aspect, this paper systematically reviews the recent studies on the use of (modified) SDB as adsorbents and in persulfate-based advanced oxidation processes (PS-AOPs) as catalysts for the contaminants removal from water over the past five years. Unmodified SDB not only exhibits stronger cation exchange and surface precipitation for heavy metals due to its nitrogen/mineral-rich properties, but also can provide abundant catalytic active sites for PS. An emphatic summary of how certain adsorption removal mechanisms of SDB or its catalytic performance in PS-AOPs can be enhanced by targeted regulation/modification such as increasing the specific surface area, functional groups, graphitization degree, N-doping or transition metal loading is presented. The interference of inorganic ions/natural organic matter is one of the unavoidable challenges that SDB is used for adsorption/catalytic removal of contaminants in real wastewater. Finally, this paper presents the future perspectives of SDB in the field of wastewater treatment. This review can contribute forefront knowledge and new ideas for advancing sludge treatment toward sustainable green circular economy.

Construction of metal-organic framework/polymer beads for efficient lead ions removal from water: Experiment studies and full-scale performance prediction.

Metal-organic frameworks (MOFs) show great promise in heavy metal removal; however, their applications are restricted by the poor separability and water instability. Herein, granular Zr-based MOF-polymer composite beads (MPCB(Zr)) (mean diameter âˆ¼ 1.74 mm) were synthesized using a facile dropping method, and applied on efficient lead ions (Pb(II)) removal. The as-prepared MPCB(Zr) demonstrated deep Pb(II) removal capability by reducing its concentration to âˆ¼ 0.002 mg L-1 after adsorption equilibrium at 360 min. The distribution coefficient for Pb(II) reached 8.0 × 106 mL g-1, and the theoretical adsorption capacity for Pb(II) was 144.5 mg g-1 (0.70 mmol g-1, 30 °C). The resulting MPCB(Zr) was highly selective for Pb(II), with the selectivity coefficient up to âˆ¼ 1.0-3.6 × 103 for the background cations (Na(I), K(I), Ca(II), and Mg(II)). Moreover, the MPCB(Zr) exhibited a broad working pH range (3.0-6.0) and satisfactory anti-interference to dissolved organic matters (humic acid and fuvic acid). Notably, the MPCB(Zr) also demonstrated excellent reusability with the Pb(II) removal efficiency over 99.0% after 20 cycles. Combined physicochemical characterizations unveiled that the thiol and oxygen-containing groups (e.g., hydroxyl, carboxylate) were responsible for the effective Pb(II) removal. To provide guidance for engineering application, the full-scale performance of the MPCB(Zr) under varying operation conditions was systematically evaluated via the validated pore surface diffusion model. This work provides an effective methodology to construct macroscopic MOF-polymer beads for effective Pb(II) removal, and promote the actual application of MOFs in water treatment.

Systematic understanding of char-volatile evolution and interaction mechanism during sewage sludge pyrolysis through in-situ tracking solid-state reaction and products fate.

The complexity of sludge components and the heterogeneity of pyrolysis products make it challenging to trace char-volatile evolutions and interaction mechanisms during pyrolysis. Herein, we systematically dissected the solid-state reactions and volatile dynamic variations via in-situ infrared/mass spectral probes coupled signal amplification techniques. The identification of hidden reactions was further enhanced by comparing the discrepancies in the pyrolysis of three systems: raw sludge, sludge-extracted organics, and pseudo-components of organics. A three-stage sludge pyrolysis of bond cleavage (α = 0.2-0.5), intermediates diffusion (α = 0.5-0.7), and interface interaction (α = 0.7-0.8) was proposed through solid-state reaction tracing, and the pyrolysis reaction was found to be dominated by the first two stages. The generation of reactive intermediates accelerated the collision frequency between reactants, which increased the order of solid-state reactions and raised the energy barrier from 148 to 180-261-297 kJ/mol. The temperature-response sequence of the major pyrolysis volatiles was H2O/CO2/furans/alcohols (<250 °C), amine-N/acids/ketones/esters (250-350 °C), heterocyclic-N/phenols/C2-3 (300-400 °C), CH4/aromatics/nitrile-N (350-450 °C), and CO/HCN (>450 °C). The temperature-dependent evolution of these volatiles was consistent with the variations of chars in terms of pyrolysis behaviors, reaction models, and surface characteristics. The comprehensive understanding of the staged pyrolysis pathways and the char-volatile interaction mechanisms may provide critical information for pyrolysis procedure design and product targeted regulation.

Superselective Hg(II) Removal from Water Using a Thiol-Laced MOF-Based Sponge Monolith: Performance and Mechanism.

Point-of-use (POU) devices with satisfying mercury (Hg) removal performance are urgently needed for public health and yet are scarcely reported. In this study, a thiol-laced metal-organic framework (MOF)-based sponge monolith (TLMSM) has been investigated for Hg(II) removal as the POU device for its benchmark application. The resulting TLMSM was characterized by remarkable chemical resistance, mechanical stability, and hydroscopicity (>2100 wt %). Importantly, the TLMSM has exhibited high adsorption capacity (∼954.7 mg g-1), fast kinetics (kf ∼ 1.76 × 10-5 ms-1), broad working pH range (1-10), high selectivity (Kd > 5.0 × 107 mL g-1), and excellent regeneration capability (removal efficiency >90% after 25 cycles). The high applicability of TLMSM in real-world scenarios was verified by its excellent Hg(II) removal performance in various real water matrices (e.g., surface waters and industrial effluents). Moreover, a fixed-bed column test demonstrated that ∼1485 bed volumes of the feeding streams (∼500 µg L-1) can be effectively treated with an enrichment factor of 12.6, suggesting the great potential of TLMSM as POU devices. Furthermore, the principal adsorption complexes (e.g., single-layer -S-Hg-Cl and double-layer -S-Hg-O-Hg-Cl and -S-Hg-O-Hg-OH) formed during the adsorption process under a wide range of pH were synergistically and systematically unveiled using advanced tools. Overall, this work presents an applicable approach by tailoring MOF into a sponge substrate to achieve its real application in heavy metal removal from water, especially for Hg(II).

Characterization of the trophic transfer and fate of methylmercury in the food web of Zhalong Wetland, Northeastern China.

The transfer and fate of methylmercury (MeHg) in typical components, such as sediment, sediment-inhabiting animals, pelagic fish, and three large waterfowls, namely, red-crowned crane (Grus japonensis), mallard (Anas platyrhynchos), and oriental stork (Ciconia boyciana), of the ecosystem in China's Zhalong Wetland were examined using equivalence-based mass balance model. The biomagnification degree of MeHg increased on the species at the high trophic level of the system. Hence, elevated MeHg concentration (3.2 µg g-1, dry weight) was detected in the endangered G. japonensis. The accumulation of the organometal generally followed the decreasing order of oriental stork (carnivore) > mallard (omnivore) > red-crowned crane (omnivore). The predicted results of MeHg at each node of the food web were generally in accordance with the measured values (F = 0.09, P = 0.78), implying that the model is suitable for the prediction of MeHg fate in the inland aquatic system. According to the model, the respiration for the species at low trophic strata was the key input source of MeHg, but ingestion played an important role for MeHg intake in the species at the high trophic position in the food web. Metabolism was a crucial pathway of MeHg loss for the top predators in the ecosystem.