Salvinia natans-Based Hierarchical Structures for Solar Thermal Clean Water Production from High-Salinity Wastewater.

Biomaterial-based solar-driven evaporation has great potential for wastewater treatment and seawater desalination with a high energy conversion and utilization efficiency. However, technology gaps still exist for effectively and directly applying multiscale structures and intrinsic water transport channels of natural materials to enhance high-efficiency photothermal evaporation. In this study, a high-performance biomass-derived photothermal evaporative material was obtained using Salvinia natans, a common aquatic floating plant, together with simple poly(m-phenylenediamine) oxidation modification, building a hybrid biomass evaporator. With advantageous natural features of adequate water transport, microscale-nanoscale hierarchical structures, effective water activation, and antisalt-fouling function, the hybrid biomass evaporator achieves a high evaporation rate of 2.24 kg m-2 h-1 under one sun radiation (1 kW m-2). In addition, modified Salvinia natans also demonstrate certain ability to remove heavy metals during the photothermal evaporation of wastewater. This work offers a new perspective on the synthesis of an environmentally friendly and cost-effective solar-driven evaporator material, which has the advantages of low cost, simple process, and high photothermal conversion efficiency, and can be widely applied to seawater desalination and the treatment of wastewater with high salt concentrations.

Smart Wrinkled Interfaces: Patterning, Morphing, and Coding of Polymer Surfaces by Dynamic Anisotropic Wrinkling.

In contrast to traditional static surfaces, smart patterned surfaces with periodical and reversible morphologies offer limitless opportunities for encoding surface functions and properties on demand, facilitating their widespread application as functional building blocks in various devices. Advances in intelligently controlling the macroscopic properties of these smart surfaces have been accomplished through various techniques (such as three-dimensional printing, imprint lithography and femtosecond laser) and responsive materials. In contrast to the sophisticated techniques above, dynamic anisotropic wrinkling, taking advantage of dynamic programmable manipulation of surface wrinkling and its orientation, offers a powerful alternative for fabricating dynamic periodical patterns due to its spontaneous formation, versatility, convenient scale-up fabrication, and sensitivity to various stimuli. This review comprehensively summarizes recent advances in smart patterned surfaces with dynamic oriented wrinkles, covering design principles, fabrication techniques, representative types of physical and chemical stimuli, as well as fine-tuning of wrinkle dimensions and orientation. Finally, advanced applications of these smart patterned surfaces are presented, along with a discussion of current challenges and future prospects in this rapidly evolving field. This review would offer some insights and guidelines for designing and engineering novel stimuli-responsive smart wrinkled surfaces, thereby facilitating their sustainable development and progressing toward commercialization.

Rethinking time-lagged emissions and abatement potential of fluorocarbons in the post-Kigali Amendment era.

The Montreal Protocol has been successful in safeguarding the ozone layer and curbing climate change. However, accurately estimating and reducing the time-lagged emissions of ozone-depleting substances or their substitutes, such as produced but not-yet-emitted fluorocarbon banks, remains a significant challenge. Here, we use a dynamic material flow analysis model to characterize the global stocks and flows of two fluorocarbon categories, hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs), from 1986 to 2060. We assess emission pathways, time-lagged emission sizes, and potential abatement measures throughout different life cycle stages while focusing on the role of banked fluorocarbons in global and regional decarbonization efforts in the post-Kigali Amendment era. Although fluorocarbon releases are expected to decline, the cumulative global warming potential (GWP)-weighted emissions of HCFCs and HFCs are significant; these will be 6.4 (±1.2) and 14.8 (±2.5) gigatons CO2-equivalent, respectively, in 2022-2060 in our business-as-usual (BAU) scenario. Scenario analysis demonstrates that implementing currently available best environmental practices in developed economies can reduce cumulative GWP-weighted emissions by up to 45% compared with the BAU scenario.

Effects of potassium-mediated electrical communication inhibition on nitrogen removal in microbial fuel cells.

Potassium ion signaling mediates microbial communication in electroactive biofilms within microbial fuel cells (MFCs), but its role in nitrogen removal remains unclear. This study investigated the impact of inhibiting potassium signaling on nitrogen removal in MFCs using tetraethylammonium chloride (TEA) as an inhibitor. Results demonstrated that 5 mM and 10 mM TEA reduced the maximum power generation of MFCs from 77.95 mW/cm2 to 57.18 mW/cm2 and 48.23 mW/cm2, respectively. Correspondingly, total nitrogen (TN) removal efficiency was decreased from 46.57 ± 1.01% to 35.93 ± 0.63% and 38.97 ± 0.74%, respectively. This decline was attributed to inhibited potassium ion signaling, which compromised the electrochemical performance of the MFC and hindered the nitrogen removal process. The relative abundance of exoelectrogen Geobactor decreased from 15.37% to 5.17% and 8.05%, while the relative abundance of cathodic nitrifying bacteria Nitrosomonas decreased from 17.87% to 4.92% and 3.63% under 5 mM and 10 mM TEA. These findings underscore the crucial role of potassium ion signaling in enhancing the bioelectrochemical nitrogen removal process in MFCs.

c-di-GMP and AHL signals-triggered chemical communication under electrical signaling disruption restores Geobacter sulfurreducens biofilm formation.

Electrogenic biofilms, which have attracted considerable attention in simultaneous wastewater treatment and energy recovery in bioelectrochemical systems, are regulated by chemical communication and potassium channel-mediated electrical signaling. However, how these two communication pathways interact with each other has not been thoroughly investigated. This study first explored the roles of chemical communication, including intracellular bis-(3'-5')-cyclic dimeric guanosine monophosphate (c-di-GMP) and extracellular N-acyl-homoserine lactone (AHL)-mediated quorum sensing, in electrogenic biofilm formation through an integrated analysis of transcriptomics and metabolomics. Electrical signaling disruption inhibited the formation and electroactivity of Geobacter sulfurreducens biofilm, which was mainly ascribed to the reduction in biofilm viability and extracellular protein/polysaccharide ratio. The upregulation of expression levels of genes encoding c-di-GMP and AHL synthesis by transcriptomic analysis, and the increased secretion of N-butanoyl-L-homoserine lactone by metabolomic analysis confirmed the enhancement of chemical communication under electrical signaling disruption, thus indicating a compensatory mechanism among different signaling pathways. Furthermore, protein-protein interaction network showed the convergence of different signaling pathways, with c-di-GMP-related genes acting as central bridges. This study highlights the interaction of different signaling pathways, especially the resilience of c-di-GMP signaling to adverse external stresses, thereby laying the foundation for facilitating electrogenic biofilm formation under adverse conditions in practical applications.

Flexible electronics for heavy metal ion detection in water: a comprehensive review.

Flexible electronics offer a versatile, rapid, cost-effective and portable solution to monitor water contamination, which poses serious threat to the environment and human health. This review paper presents a comprehensive exploration of the versatile platforms of flexible electronics in the context of heavy metal ion detection in water systems. The review overviews of the fundamental principles of heavy metal ion detection, surveys the state-of-the-art materials and fabrication techniques for flexible sensors, analyses key performance metrics and limitations, and discusses future opportunities and challenges. By highlighting recent advances in nanomaterials, polymers, wireless integration, and sustainability, this review aims to serve as an essential resource for researchers, engineers, and policy makers seeking to address the critical challenge of heavy metal contamination in water resources. The versatile promise of flexible electronics is thoroughly elucidated to inspire continued innovation in this emerging technology arena.

π-π Stacking at the Perovskite/C60 Interface Enables High-Efficiency Wide-Bandgap Perovskite Solar Cells.

Interface passivation is a key method for improving the efficiency of perovskite solar cells, and 2D/3D perovskite heterojunction is the mainstream passivation strategy. However, the passivation layer also produces a new interface between 2D perovskite and fullerene (C60), and the properties of this interface have received little attention before. Here, the underlying properties of the 2D perovskite/C60 interface by taking the 2D TEA2PbX4 (TEA = C6H10NS; X = I, Br, Cl) passivator as an example are systematically expounded. It is found that the 2D perovskite preferentially exhibits (002) orientation with the outermost surface featuring an oriented arrangement of TEACl, where the thiophene groups face outward. The outward thiophene groups further form a strong π-π stacking system with C60 molecule, strengthening the interaction force with C60 and facilitating the creation of a superior interface. Based on the vacuum-assisted blade coating, wide-bandgap (WBG, 1.77 eV) perovskite solar cells achieved impressive records of 19.28% (0.09 cm2) and 18.08% (1.0 cm2) inefficiency, respectively. This research not only provides a new understanding of interface processing for future perovskite solar cells but also lays a solid foundation for realizing efficient large-area devices.

Formation mechanism of persistent free radicals during pyrolysis of Fenton-conditioned sewage sludge: Influence of NOM and iron.

The present study provided an innovative insight into the formation mechanism of persistent free radicals (PFRs) during the pyrolysis of Fenton-conditioned sludge. Fenton conditioners simultaneously improve the dewatering performance of sewage sludge and catalyze the pyrolysis of sewage sludge for the formation of PFRs. In this process, PFRs with a total number of spins of 9.533×1019 spins/g DS could be generated by pyrolysis of Fenton-conditioned sludge at 400°C. The direct thermal decomposition of natural organic matter (NOM) fractions contributed to the formation of carbon-centered radicals, while the Maillard reaction produced phenols precursors. Additionally, the reaction between aromatic proteins and iron played a crucial role in the formation of phenoxyl or semiquinone-type radicals. Kinetics analysis using discrete distributed activation energy model (DAEM) demonstrated that the average activation energy for pyrolysis was reduced from 178.28 kJ/mol for raw sludge to 164.53 KJ/mol for Fenton conditioned sludge. The reaction factor (fi) indicated that the primary reaction in Fenton-conditioned sludge comprised of 27 parallel first-order reactions, resulting from pyrolysis cleavage of the NOM fractions, the Maillard reaction, and iron catalysis. These findings are significant for understanding the formation process of PFRs from NOM in Fenton-conditioned sludge and provide valuable insight for controlling PFRs formation in practical applications.

Visualization of water transfer channel in sludge dewatering conditioned with skeleton builders by X-ray micro-computed tomography.

Skeleton builders were normally deemed to improve the high porosity and newly-generated permeability of sludge cakes by building water transfer channel during high pressure filtration, thus enhancing sludge dewaterability. However, currently a direct visualization proof of water transfer channel was still lacking. This study provided the direct proof for visualizing water transfer channel in dewatered sludge cakes conditioned with a typical skeleton builder (i.e., phosphogypsum (PG)) by X-ray micro-computed tomography (micro-CT) for the first time. After the addition of PG, the pixel value and image luminance increased significantly, indicating the presence of high density substances from both two-dimensional (2D) cross section and three-dimensional (3D) reconstruction CT images. Moreover, the CT numbers showed strong and negative correlations with specific resistance to filtration (SRF) (R = - 0.99, p < 0.05), capillary suction time (CST) (regression coefficient (R) = - 0.87, probability (p) < 0.05), and water content of the dewatered sludge cake (R = - 0.99, p < 0.05), respectively. These results indicated that the X-ray micro-CT could be a potential technique for analyzing the water distribution in sludge samples conditioned with skeleton builders.

Peroxymonosulfate activation by trace iron(III) porphyrin for facile degradation of organic pollutants via nonradical oxidation.

Nonradical species with great resistance to interference have shown great advantages in complex wastewater treatment. Herein, a novel system constructed by biodegradable tetrakis-(4-carboxyphenyl)-porphyrinatoiron(III) (FeIII-TCPP) and peroxymonosulfate (PMS) was proposed for facile decontamination. Nonradical pathway is observed in FeIII-TCPP/PMS, where 1O2 and high-valent iron-oxo species play dominant roles. The genres and valence of high-valent iron-oxo species, including iron(IV)-oxo porphyrin radical-cationic species [OFeIV-TCPP•+] and iron(IV)-hydroxide species [FeIV-TCPP(OH)], are ascertained, along with their generation mechanism. The axial ligand on the iron axial site affects the ground spin state of FeIII-TCPP, further influencing the thermodynamic reaction pathway of active species. With trace catalyst in micromoles, FeIII-TCPP exhibits high efficiency by degrading bisphenol S (BPS) completely within 5 min, while Co2+/PMS can only achieve a maximum of 26.2% under identical condition. Beneficial from nonradical pathways, FeIII-TCPP/PMS demonstrates a wide pH range of 3-10 and exhibits minimal sensitivity to interference of concomitant materials. BPS is primarily eliminated through ß-scission and hydroxylation. Specifically, 1O2 electrophilically attacks the C-S bond of BPS, while high-valent iron-oxo species interacts with BPS through an oxygen-bound mechanism. This study provides novel insights into efficient activation of PMS by iron porphyrin, enabling the removal of refractory pollutants through nonradical pathway.

Molecular mechanisms and physiological responses of rice leaves co-exposed to submicron-plastics and cadmium: Implication for food quality and security.

The effects of co-exposure to aged submicron particles (aSMPs) and Cd as model contaminants on rice leaves via the foliar route were investigated. Thirty-day-old rice seedlings grown in soil were exposed to Cd (nitrate) through foliar spraying at concentrations of 1, 10, 50, 100, and 500 µM, with or without aSMP at a rate of 30 µg d-1. It was observed that Cd translocated from leaves to roots via stems even without co-exposure to SMP. Co-exposure can reduce cadmium levels in leaves. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis confirmed a significant reduction (29.3 - 77.9%) in Cadmium accumulation in the leaves of rice plants during co-exposure. Exposure to Cd resulted in physiological, transcriptomic, and metabolomic changes in rice leaves, disrupting 28 metabolism pathways, and impacting crop yield and quality. Exposure to both Cd and aSMPs can interfere with the Cd distribution in plants. Rice leaves exposed solely to Cd exhibit higher toxicity and Cd accumulation, compared to those co-exposed to Cd and aSMPs. The accumulation of Cd in plant leaves is enhanced with aSMPs, which may lead to more pronounced gene expression regulation and changes in metabolic pathways, compared to Cd exposure. Our study found that the independent Cd exposure group had higher Cd accumulation and toxicity in rice leaves compared to the combined exposure of Cd and aSMPs. We hypothesize that aged negatively charged SMPs can capture Cd and reduce its exposure in the free state while jointly inhibiting Cd-induced oxidative and chloroplast damage, thereby reducing the potential risk of Cd exposure in rice plants.

Numerical simulation to optimize passive aeration strategy for semi-aerobic landfill.

Passive aeration has been proven to be efficient for oxygen supply in landfill. The combination of passive aeration and semi-aerobic landfill offers a cost-effective and energy-efficient approach to solid waste (SW) treatment. However, determining the optimal strategy for this combination has remained unclear. This study aimed to investigate the strategy of passive aeration in a semi-aerobic landfill using numerical simulation methods. A model coupled hydrodynamic model and compartment model for degradation of SW was implemented. The accuracy was well validated by comparing measured and simulated results in a pilot-scale landfill. Compared with natural convection, passive aeration by funnel caps could increase air input by 20 %. By simulating volumetric fraction distribution of CO2, CH4 and O2 in landfill, an orthogonal experiment including 4 factors was designed to identify that the diameter of tubes (DT), the spacing between tubes (ST) and the landfill depth (LD) have substantial impacts on aerobic zone ratio (AZR) of landfill. But the diameter of gas ports (DGP) has an indiscernible effect. The optimized factors were determined to be as follows: DT = 0.3 m, ST = 15.0 m, DGP = 0.05 m, and LD = 4.0 m, under which the semi-aerobic landfill could enhance SW degradation. Large diameter and spacing of tubes are favorable to improve the AZR at the top of the landfill, and the aerobic zone mainly exists near the ventilation tubes. These findings contribute to the development of more efficient and sustainable solid waste treatment strategies in semi-aerobic landfill.

Sludge-derived iron-carbon material enhancing the removal of refractory organics in landfill leachate: Characteristics optimization, removal mechanism, and molecular-level investigation.

Mature landfill leachate is a refractory organic wastewater, and needs physical and chemical pretreatments contemporaneously, e.g. iron-carbon micro-electrolysis (IC-ME). In this study, a novel iron-carbon (Fe-C) material was synthesized from waste activated sludge to be utilized in IC-ME for landfill leachate treatment. The pyrolysis temperature, mass ratio of iron to carbon, and solid-liquid ratio in leachate treatment were optimized as 900 °C with 1.59 and 34.7 g/L. Under these optimal conditions, the chemical oxygen demand (COD) removal efficiency reached 79.44 %, which was 2.6 times higher than that of commercial Fe-C material (30.1%). This excellent COD removal performance was indicated to a better mesoporous structure, and uniform distribution of zero-valent iron in novel Fe-C material derived from sludge. The contribution order of COD removal in IC-ME treatment for landfill leachate was proven as coagulation, adsorption, and redox effects by a contrast experiment. The removal of COD includes synthetic organic compounds, e.g. carcinogens, pharmaceuticals and personal care products. The contents of CHO, CHON, and CHOS compounds of dissolved organic matter (DOM) in the leachate were decreased, and both the molecular weight and unsaturation of lipids, lignin, and tannic acids concentration were also reduced. Some newly generated small molecular DOM in the treated leachate further confirmed the existence of the redox effect to degrade DOM in leachate. The total cost of sludge-derived Fe-C material was only USD$ 152.8/t, which could save 76% of total compared with that of commercial Fe-C materials. This study expands the prominent source of Fe-C materials with excellent performance, and deepens the understanding of its application for leachate treatment.

Behavior of organic components and the migration of heavy metals during sludge dewatering by different advanced oxidation processes via optical spectroscopy and molecular fingerprint analysis.

A comparative study of the different advanced oxidation processes (Fe(II)-Oxone, Fe(II)-H2O2, and Fe(II)-NaClO) was carried out herein to analyze the characteristics of organic components and the migration of heavy metals in waste activated sludge. With the Fe(II)-Oxone and Fe(II)-H2O2 treatments, sludge dewaterability was significantly improved, however, sludge dewaterability was deteriorated by the Fe(II)-NaClO treatment. The enhanced sludge dewaterability by the Fe(II)-Oxone and Fe(II)-H2O2 treatments was strongly correlated with the shifted organic components, particularly proteins, in soluble extracellular polymeric substances (S-EPS), while the deteriorated sludge dewaterability by the Fe(II)-NaClO treatment was strongly correlated with the over release of organic components from bound EPS (B-EPS) to S-EPS. For both the Fe(II)-Oxone and Fe(II)-H2O2 treatments, the radicals preferentially attacked humic acid-like organic components over the protein-like organic components in S-EPS, while for the Fe(II)-NaClO treatment, interestingly, the radicals preferentially attacked the protein-like organic components in both S-EPS and B-EPS. The hydrophilic functional groups like phenolic OH and CO of polysaccharides may be more preferentially migrated to S-EPS of sludge by the Fe(II)-NaClO treatment compared to the other two treatments. With the Fe(II)-Oxone and Fe(II)-H2O2 treatments, the proportion of aliphatic compounds as well as the much oxygenated organic components with a low desaturation and a low molecular weight increased. While with the Fe(II)-NaClO treatment, the proportion of low oxygenated organic components with a high desaturation and a high molecular weight increased. The concentration of total organic carbon, particularly the concentration of proteins, may be the key factor determining the shift of Zn and Cu from sludge solid to liquid phase, along with the high oxidation extent of organic components and close binding to CHOS and CHON compounds as indicated by density functional theory (DFT) calculation. This study systematically revealed the simultaneous sludge dewatering and migration of heavy metals when the role of organic components was factored into herein.

Revealing the roles of chemical communication in restoring the formation and electroactivity of electrogenic biofilm under electrical signaling disruption.

Electrogenic biofilms in microbial electrochemical systems have played significant roles in simultaneous wastewater treatment and energy recovery owing to their unique extracellular electron transfer. Their formation has been shown to be regulated by electrical and chemical communication, but the interaction between these signal communication pathways has not been studied. This research investigated the coordination between intracellular c-di-GMP signaling and reinforced quorum sensing with or without exogenous HSL (a common quorum sensing molecule), on the formation of mixed-cultured electrogenic biofilm under electrical signaling disruption by tetraethylammonium (TEA, a broad-range potassium channel blocker). Intracellular c-di-GMP was spontaneously reinforced in response to TEA stress, and metagenomic analysis revealed that the dominant DGC (the genes for producing c-di-GMP) induced the eventual biofilm formation by mediating exopolysaccharide synthesis. Meanwhile, reinforced quorum sensing by exogenous HSL could also benefit the biofilm restoration, however, it alleviated the TEA-induced communication stress, resulting in the weakening of c-di-GMP dominance. Interestingly, suppressing electrical communication with or without HSL addition both induced selective enrichment of Geobacter of 85.5% or 30.1% respectively. Functional contribution analysis revealed the significant roles of Geobacter and Thauera in c-di-GMP signaling, especially Thauera in resistance to TEA stress. This study proposed a potential strategy for electrogenic biofilm regulation from the perspectives of cell-to-cell communication.

Peroxymonosulfate activated by natural porphyrin derivatives for rapid degradation of organic pollutants via singlet oxygen and high-valent iron-oxo species.

The activation of peroxymonosulfate (PMS) by sodium ferric chlorophyllin (SFC), a natural porphyrin derivative extracted from chlorophyll-rich substances, was systematically investigated for facile degradation of bisphenol A (BPA). SFC/PMS is capable of degrading 97.5% of BPA in the first 10 min with the initial BPA concentration of 20 mg/L and pH = 3, whereas conventional Fe2+/PMS could only remove 22.6% of BPA under identical conditions. It demonstrates a prominent flexibility to a broad pH range of 3-11 with complete pollutant degradation. A remarkable tolerance toward concomitant high concentration of inorganic anions (100 mM) was also observed, among which (bi)carbonates can even accelerate the degradation. The nonradical oxidation species, including high-valent iron-oxo porphyrin species and 1O2, are identified as dominant species. Particularly, the generation and participation of 1O2 in the reaction is evidenced by experimental and theoretical methods, which is vastly different from the previous study. The specific activation mechanism is unveiled by density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations. The results shed light on effective PMS activation by iron (III) porphyrin and the proposed natural porphyrin derivative would be a promising candidate for efficient abatement of recalcitrant pollutants toward complicated aqueous media in wastewater treatment.

Novel PbO@C composite material directly derived from spent lead-acid batteries by one-step spray pyrolysis process.

A one-step spray pyrolysis process is investigated for the first time in the field of spent lead-acid batteries (LABs) recycling. The spent lead paste that derived from spent LAB is desulfurized and then leached to generate the lead acetate (Pb(Ac)2) solution, which is then sprayed directly into a tube furnace to prepare the lead oxide (PbO) product by pyrolysis. The low-impurity lead oxide product (9 mg/kg Fe and 1 mg/kg Ba) is obtained under the optimized conditions (the temperature of 700 °C, the pumping rate of 50 L/h, and the spray rate of 0.5 mL/min). The major crystalline phases of the synthesized products are identified to be α-PbO and ß-PbO. In the spray pyrolysis process, Pb(Ac)2 droplets are sequentially transformed into various intermediate products: H2O(g)@Pb(Ac)2 solution, Pb(Ac)2 crystals@PbO, and the final PbO@C product. Owning its carbon skeleton structure, the recovered PbO@C product (carbon content of 0.14%) shows better performance than the commercial ball-milled lead oxide powder in battery tests, with higher initial capacity and better cycling stability. This study could provide a strategy for the short-route recovery of spent LABs.