Lead contamination poses a serious threat to aquatic environments and human health, while the limited metal-binding affinity of native cellulose restricts its direct application in Pb(II) remediation. Herein, a series of carboxylated cellulose/δ-MnO2 composite adsorbents (MCC-Mnx, x = 1-4) were constructed through a one-step KMnO4 oxidation strategy, thereby overcomes the limited Pb(II) affinity of native cellulose by integrating cellulose oxidation and in situ δ-MnO2 nanosheet formation. During this process, KMnO4 partially oxidized MCC surface hydroxyls into carboxyl-containing groups, increased surface negativity and altered the local hydrogen-bonding environment, accompanied by an increase in specific surface area and active-site accessibility. The in situ formed birnessite-type δ-MnO2 nanosheets exposed oxygen-active (002) facets and provided abundant Mn-O/Mn-OH sites, jointly promoting Pb(II) immobilization through electrostatic attraction, surface complexation, and ion exchange. Among the prepared materials, MCC-Mn2 achieved rapid Pb(II) uptake within 60 min and a high Langmuir maximum adsorption capacity of 1176.15 mg·g-1 at 318 K. The adsorbent maintained preferential Pb(II) adsorption in a quaternary metal system containing Pb(II), Cd(II), Co(II), and Cu(II), and retained 88.6% removal efficiency after five regeneration cycles. This study provides a scalable strategy for designing high-performance cellulose-based metal oxide adsorbents for heavy-metal remediation from wastewater.
Soil contaminated with polycyclic aromatic hydrocarbons (PAHs) increasingly threatens environmental safety and ecosystem health. Catalyst-activated persulfate advanced oxidation processes have shown great promise for remediating such soils, especially Fe-C composite catalysts that combine the activation properties of both Fe and C. However, their complex and costly preparation has limited its practical application. In this work, magnetic steelmaking dust (BFD-M), rich in Fe and C and derived from blast furnace processes, was utilized as a low-cost and sustainable precursor for Fe-C catalyst synthesis. Furthermore, an energy-efficient ball milling-persulfate pretreatment was employed to enhance the reactivity of BFD-M and simplify the catalyst preparation process. The resulting catalyst (BFD-MBS) can efficiently activate persulfate, achieving 91.06 % removal of phenanthrene (a representative PAH) from contaminated soil. This efficient degradation was driven by the synergistic action of multiple reactive oxygen species (ROS), including SO center dot- oxidation mechanism enabled by BFD-MBS. ROS generation was attributed to the cooperative persulfate activation by Fe oxides (Fe2O3 and Fe3O4) and functionalized C structures (C-OH, -COOH, and defects) on BFD-MBS surface, especially the Fe-O-C interface. After the catalytic reaction, most degradation intermediates were less hazardous than the parent compound and no detectable release of heavy metals was observed, confirming the environmental safety of the catalytic system. Overall, this work presents a promising strategy for converting steelmaking waste into persulfate catalysts targeting PAH-contaminated soil remediation, contributing to the sustainable development of both the steel industry and environmental remediation.
We developed a multi-stage flocculation reactor (MFR) featuring a graded configuration of strong, moderate, and weak mixing zones to address the distinct hydrodynamic requirements at different flocculation stages. This study focused on the strong mixing segment, investigating flocculant diffusion, initial floc formation, and subsequent growth behavior to elucidate its role in overall floc development. Experimental results demonstrated that increasing inlet flow velocity from 0.29 m/s to 0.49 m/s reduced flocculant mixing time in the strong mixing segment from 1.133 s to 0.380 s. Correspondingly, the average chord length of primary flocs increased from 63 & micro;m to 102 & micro;m, and their fractal dimension (Df) rose from 1.4583 to 1.5481. The final floc size also improved from 150 & micro;m to 238 & micro;m, accompanied by an increase in Df from 1.6655 to 1.9320. However, when the inlet velocity reached 0.69 m/s, although the mixing time further decreased to 0.273 s and the primary flocs expanded to 127 & micro;m with a Df of 1.6201, the final floc size decreased to 185 & micro;m and the Df declined to 1.8149. These findings indicate that appropriate energy input in the strong mixing segment promotes flocculant diffusion and primary floc formation, thereby improving the final floc size and compactness. In contrast, excessive energy input produces overly dense primary floc surfaces with fewer active binding sites, hindering subsequent aggregation and ultimately impairing flocculation performance. This work elucidates the dual function of the strong mixing segment in floc formation and provides theoretical guidance for flocculation reactor design.
Complex oily wastewater typically contains both surfactant-stabilized oil droplets and dissolved organic pollutants, requiring a membrane material capable of efficient interfacial separation and catalytic pollutant removal. In this work, coal fly ash (CFA) was used as a low-cost aluminum source to construct hierarchical AlOOH@TiO2 nanoflowers. These were immobilized on a nylon substrate via a bilayer polydopamine/polyethyleneimine (PDA/PEI) structure to fabricate a sandwich-structured membrane. The lower layer PDA/PEI network strengthened AlOOH@TiO2 nanoflower adhesion to the nylon substrate, whereas the upper layer network inhibited AlOOH@TiO2 shedding. Amino groups in PDA/PEI and hydroxyl groups on AlOOH@TiO2 rendered the membrane superhydrophilic/underwater oleophobic, with an underwater oil contact angle of 161.2 ± 0.2°. The open nanoflower structure enabled a maximum membrane permeance of 5200 L m-2 h-1 bar-1. Based on hydration-layer effects, electrostatic repulsion, and steric hindrance, the membrane achieved over 99.9% separation efficiency for surfactant-stabilized oil-in-water emulsions. Additionally, the membrane remained stable after repeated filtration and after acidic, alkaline, and saline conditions. Under 365 nm UV irradiation, the membrane removed 99.1% of methylene blue within 1 h, owing to UV response of TiO2 and heterointerface-promoted photocarrier separation. This study demonstrates a sustainable strategy for converting CFA into a robust dual-functional membrane for integrated emulsion separation and photocatalytic purification.
Oil/water separation materials are easily damaged by low-surface-energy, high-viscosity oil contaminants, severely restricting their application in treating oil-containing wastewater. In this study, we enhanced the antifouling capability of the coating through ultrasonic assistance to achieve stable separation of water-in-oil (W/O) emulsions. A robust superhydrophobic mesh was developed by spraying octadecyltrichlorosilane (ODTMS) modified silica onto stainless steel mesh. By placing an ultrasonic probe onto the surface of the ODTMS@SiO2 coating, an ultrasonic-assisted oil/water separation system was constructed. Under ultrasonic assistance, the fouling of the ODTMS@SiO2coating was alleviated due to mechanical vibration, which helped the physical removal of adhesive oil droplets from the surface and internal pores. When ultrasonic probe with frequency of 50 kHz was applied to the coating surface, a flux up to 6004 L m-2 h-1 with separation efficiency above 99.9 % for W/O emulsions was achieved, approximately 2.3 times higher than that without ultrasound assistance. Under ultrasonic assistance, the coating demonstrated stable high permeation flux with a low flux decline rate of 3 % for surfactant-stabilized W/O emulsions. After ultrasonic treatment of the oil-contaminated coating, the flux can recover nearly 100 %. This integrated system offered a robust, high-capacity, and environmentally friendly approach for the treatment of industrial oily wastewater.
This study investigates the desorption behavior of a representative petroleum pollutant, phenanthrene (Phe), from typical soil minerals including quartz sand, montmorillonite, kaolinite, and illite. By integrating molecular dynamics simulations with multiscale batch experiments, we systematically explore how mineral interfacial properties and surfactant interactions govern desorption mechanisms. Results show that pore structure plays a dominant role: in deionized water, montmorillonite-with a mesoporous structure (18.29 nm) and high surface area (28.00 m2/g)-achieved a desorption rate of 24.0 %, while kaolinite, limited by its smaller pore size (6.13 nm), released only 12.9 %. Three types of surfactants (CTAB, SDS, and Tween 80) were evaluated for their desorption-enhancing effects. Among them, SDS significantly promoted desorption via a synergistic mechanism combining electrostatic repulsion and micelle solubilization, increasing Phe desorption from montmorillonite to 87.8 %. Additionally, surfactant addition effectively reduced the interfacial binding energy between Phe and mineral surfaces-from -32.00 to -18.13 kJ/mol-overcoming the energy barrier to desorption. Molecular simulations further revealed distinct Phe adsorption conformations across different minerals, aligning well with observed macroscopic behaviors. Based on these findings, a coupled multiscale model was developed linking interfacial energy, pore-scale mass transfer, and macroscopic desorption kinetics. This framework offers practical guidance for selecting surfactant types, optimizing concentration gradients, and tuning mechanical agitation parameters in the remediation of petroleum-contaminated sites, with strong potential for engineering application.
The treatment of steelmaking wastes, particularly blast furnace dust (BFD), presents challenges for steel plants. Rich in iron (Fe) and carbon (C), BFD has potential for reuse. This study systematically investigated the surface microstructure of BFD's magnetic fraction (BFD-M) and its role in enhancing persulfate (PS) catalysis for pollutant degradation. Key catalytic molecular fragments were also identified, providing theoretical insights for further optimizing preparation of BFD-based PS catalysts. The result showed that Fe in BFD-M is primarily Fe3O4 or Fe2O3, while C contains abundant oxygen-containing functional groups and defects. All these catalyze PS to degrade organic pollutants. Surface dispersions of Fe oxides on C substrate increase catalytic site exposure compared to their independent form, while embedding prevents sites loss. Electrostatic potential calculations reveal that oxygen-containing groups, defects, and Fe-O-C structures disrupt the chemical inertness of C substrate, promoting electron transfer and enhancing PS activation. Especially the Fe-O-C exhibit pronounced electron enrichment. The strong interaction between Fe and C increases the formation of C defects, which can enhance PS catalysis and promote Fe3+/Fe2+ cycling, addressing a common limitation of Fe-based catalysts. These findings can provide theoretical guidance for BFD's innovative applications in pollutants degradation, promoting co-development of steelmaking and environmental remediation.
Water pollution is a global challenge, and catalytic activation of persulfate in advanced oxidation processes offers an effective solution for treating organic wastewater. However, the complex preparation of persulfate catalysts limits their widespread adoption, while eco-friendly disposal of blast furnace dust (BFD) remains a challenge for the steel industry. This work addresses both issues by developing a BFD-derived catalyst for phenanthrene (PHE) degradation in wastewater. Under optimal conditions (0.5 g/L catalyst, 2 mM oxidant, and no pH adjustment at room temperature), the system achieved 90.36 % PHE removal from wastewater. This excellent removal efficiency is attributed to the synergistic action of SO center dot 4 , SO center dot 5, center dot OH, O center dot 2 and 1O2, with the high-redox-potential species SO center dot 4 and center dot OH being the primary contributors, accounting for 52.31 % of the removal efficiency. The Fe-O-C played a crucial role in their production by promoting O-O bond cleavage in SP. Additionally, this system also exhibited a unique oxygen generation effect and an efficient Fe3+/Fe2+ cycling mechanism, essential for maintaining high catalytic performance. The minimal metal Fe leaching (<= 0.001 mg/L) confirms the catalyst's stability, with a PHE removal efficiency of 80.20 % maintained in the fifth cycle. Toxicity assessments revealed that most degradation intermediates had lower toxicity than phenanthrene, indicating the system's effectiveness in reducing environmental hazards. This work provides a promising catalyst for persulfate and suggests a new avenue for the resource utilization of steel waste, supporting the sustainable development of both environmental remediation and steel industry.
Intelligent materials demonstrate promising applications in switchable oil/water separations. A stearic acid (SA) hydrophobically modified SiO2 coating (SA/SiO2) with switchable wettability was developed by simply spraying. The SA/SiO2 coating with micro-nanostructure showed excellent superhydrophobicity with water contact angle (WCA) and oil contact angle (OCA) of 158.7° and 0°, respectively. When the SA/SiO2 coating was contacted with ammonia, it showed excellent superhydrophilicity, with WCA and underwater oil contact angle of 0° and 155.4°, respectively. After heating treatment, the SA/SiO2 coating returned to superhydrophobicity. Through wettability switching, the prepared SA/SiO2 coating could be applied for on-demand separation of oil/water/oil ternary mixtures as well as various water-in-oil emulsions and oil-in-water emulsions, and the separation efficiency of oil-in-water emulsion could reach up to 99.97
Flocculation is a significant process in treating shale gas hydraulic fracturing flowback fluids. To achieve a high removal rate of pollutant, a range of multi-stage enhanced flocculation reactors that incorporated sequential intense, moderate, and weak mixing sections along the flow direction were devised, in which the aspect ratios (ARs) in the intense mixing section were varied. The results of the computer simulation indicated that the reactor with AR of 3.5 exhibited a gradual decrease in velocity and energy along the flow direction, and the flow field distribution is highly uniform and symmetrical. The generated flow field promoted the formation of small flocs in the intense mixing section and facilitated the collision of small flocs in the moderate mixing section, while preventing the fragmentation of flocs in the weak mixing section, therefore resulting in the generation of large and compact flocs. Moreover, the generated flocs demonstrated a good resistance to shear and oscillation, facilitating their separation from the simulated flowback fluids. The obtained reactor achieved remarkable removal efficiencies of 80.15 % for COD and 89.06 % for turbidity. Furthermore, when treating bentonite sus-pension, the multi-stage flocculation reactor achieved a turbidity removal rate of 99.34 % with a processing time of only 2.38 min and a settling time of just 20 min. This demonstrated the broad applicability of this reactor to various types of wastewater. This work provides valuable insights into the design of efficient flocculation reactors by integrating multiple mixing intensities within a reactor.
Superwettable materials with switchable wettability have been attracting tremendous attention in the field of oil-water separation. In this work, a multifunctional coating with switchable wettability was designed for efficient oil-water and emulsions separation. Fe3O4 was combined with TiO2 nanoparticles and hydrophobically modified by low surface energy stearic acid (SA) to form the Fe3O4/TiO2@SA coating with uniform micro-nanostructures. The introduction or removal of amino group via ammonia treatment or heating treatment endowed the coating with reversible conversion between hydrophilicity and hydrophobicity. By switching hydrophilicity and hydrophobicity, the coating could separate oil/water/oil ternary mixtures in sequence with high separation efficiency of more than 99.9 %. More importantly, it displayed excellent separation efficiency with oil rejection above 99.5 % for oil-in-water (O/W) emulsions and water rejection above 98.7 % for water-in-oil (W/O) emulsions. Moreover, this coating showed reliable reusability and mechanical stability after 10 cycles of O/W and W/O emulsions separation and 20 cycles of sandpaper abrasion. Fe3O4 and TiO2 imparted magnetic and photocatalytic properties to the coating, allowing it to be used for magnetic navigation of oil absorption and photocatalytic degradation of organic dyes. The unique features of multifunctional coating with switchable wettability provide the blueprint for treating oily wastewater and marine oil spills.
Petroleum-contaminated soil (PCS) poses a significant health risk. Catalyst-activated persulfate presents a promising technology for efficient treatment, while magnetic activated carbon catalysts are increasingly recognized for their easy recovery and robust performance in advanced oxidation processes (AOPs). However, the complex and costly preparation process has limited its widespread implementation. In this work, blast-furnace dust (BFD), a solid waste from steel mill, was used as a novel persulfate catalyst for the total petroleum hydrocarbons (TPHs) removal from PCS. With the BFD/SP system (0.1 g BFD and 1 mM PS for per gram soil, 4:1 water-to-soil ratio, and 40 degrees C), removal rates of 88.10% and 84.39% were achieved for TPHs in 0.7% and 3.0% PCS, respectively, surpassing most reported persulfate AOPs, highlighting its superior efficacy. The main reason was that Fe/C components on BFD surface could cooperate to cyclically produce diverse reactive oxygen species, including SO4 center dot-, OH center dot, O-2(center dot-) and O-1(2). Furthermore, the amphiphilicity of BFD could promote both pollutants and oxidants to converge to its surface simultaneously, effectively utilizing short-lived ROS to degrade TPHs. Our findings implies that BFD is an excellent SP activator, providing an innovative approach for PCS treatment and promoting sustainable utilization of BFD.
Among numerous oil-water separation materials, coalescence materials have received widespread attention. In this work, we prepared a lotus leaf-shaped Janus coalescing material by physically mixing polyethylene (PE) and polypropylene (PP) first, pressing it into sheets, then single-face hydrophilic modifying by chemical oxidation method, followed by pressing into a lotus leaf shape. Finally, holes were physically punched at the upper and lower sides of the coalescing material to let the oil drops pass through freely, greatly reducing the time for oil droplets to float. The shape of lotus leaves could provide more opportunities for oil droplets to collide and coalesce. The coalescing materials had asymmetric wettability, with specific surfaces that were oleophilic on the one hand and hydrophilic on the other. The oil droplets adhered to the oleophilic side of the coalescing material, coalesced and grew, then floated up and passed through the coalescing sheet layer by layer until they reached the oil collecting port to realize oil-water separation. The structural parameters of the coalescing material were progressively optimized. The obtained coalescing material exhibited a high oil-water separation efficiency of 99.40 +/- 0.5% with good stability during a 48 h continuous oil-water separation, which provided a reference for the development of efficient coalescing materials.
Flocculation plays a significant role in the treatment of shale gas hydraulic fracturing flowback fluids. To achieve high pollutant removal rates, a range of multi-stage enhanced flocculation reactors that incorporate sequential intense, moderate, and weak mixing sections along the flow direction were devised, in which the aspect ratios (ARs) in the intense mixing section were varied. The computer simulation results indicated that the reactor with AR of 3.5 exhibited a gradual decrease in velocity and energy along the flow direction, and the flow field distribution was highly uniform and symmetrical. The generated flow field promoted the formation of small flocs in the intense mixing section and facilitated the collision of small flocs in the moderate mixing section, while preventing the fragmentation of flocs in the weak mixing section, therefore resulting in the generation of large and compact flocs. Moreover, the generated flocs demonstrated good resistance to shear and oscillation, facilitating their separation from the flowback fluids. The obtained reactor achieved remarkable removal efficiencies of 80.15% for turbidity and 89.06% for COD. This work provides valuable insights for the design of efficient flocculation reactors by integrating multiple mixing intensities within a reactor.
Golden2, ARR-B, Psr1 (GARP) proteins are plant-specific transcription factors that play vital and diverse roles in plants. However, systematic research on the GARP gene family in plants, including tea plant (Camellia sinensis), is scarce. In this study, a total of 69 GARP genes were identified and characterized from the tea plant genome based on the B-motif sequence signature. The CsGARP genes were clustered into five subfamilies: PHR1/PHL1, KAN, NIGT1/HRS1/HHO, GLK and ARR-B subfamilies. The phylogenetic relationships, gene structures, chromosomal locations, conserved motifs and regulatory cis-acting elements of the CsGARP family members were comprehensively analyzed. The expansion of CsGARP genes occurred via whole-genome duplication/segmental duplication, proximal duplication, and dispersed duplication under purifying selective pressure. The expression patterns of the CsGARP genes were systematically explored from various perspectives: in different tissues during different seasons; in different leaf color stages of tea plant; under aluminum treatment and nitrogen treatment; and in response to abiotic stresses such as cold, drought and salt and to biotic stress caused by Acaphylla theae. The results demonstrate that CsGARP family genes are ubiquitously expressed and play crucial roles in the regulation of growth and development of tea plant and the responses to environmental stimuli. Collectively, these results not only provide valuable information for further functional investigations of CsGARPs in tea plant but also contribute to broadening our knowledge of the functional diversity of GARP family genes in plants.
Valosin-containing protein (VCP)/p97 is an AAA-ATPase that extracts polyubiquitinated substrates from multimeric macromolecular complexes and biological membranes for proteasomal degradation. During p97-mediated extraction, the substrate is largely deubiquitinated as it is threaded through the p97 central pore. How p97-extracted substrates are targeted to the proteasome with few or no ubiquitins is unknown. Here, we report that p97-extracted membrane proteins undergo a second round of ubiquitination catalyzed by the cytosolic ubiquitin ligase RNF126. RNF126 interacts with transmembrane-domain-specific chaperone BAG6, which captures p97-liberated substrates. RNF126 depletion in cells diminishes the ubiquitination of extracted membrane proteins, slows down their turnover, and dramatically stabilizes otherwise transient intermediates in the cytosol. We reconstitute the reubiquitination of a p97-extracted, misfolded multispanning membrane protein with purified factors. Our results demonstrate that p97-extracted substrates need to rapidly engage ubiquitin ligase-chaperone pairs that rebuild the ubiquitin signal for proteasome targeting to prevent harmful accumulation of unfolded intermediates.
For the exploration of circular RNA light chain kinase (circRNA-MYLK), siRNA#1 and siRNA#2 targeting circRNA-MYLK as well as microRNA(miR)-145-5p inhibitor were transfected. Viability was valued with the CCK-8. The protein expression was examined relying on Western blot. The expression of circRNA-MYLK or miR-145-5p was tested depending on qRT-PCR. The apoptotic/migration/invasion rate was separately measured by the Annexin v-FITC/PI with flow cytometer or chambers assays. CircRNA-MYLK was overexpressed in tumor tissue. Silencing circRNA-MYLK induced the inhibitions of viability, invasion and migration, as well as the blocks of MEK/ERK and NF-κB cascades, however, silencing circRNA-MYLK led to provoking of apoptosis. Besides, circRNA-MYLK silencing stimulated the over-production of miR-145-5p, whose silencing abolished the effects of siRNA#1 and siRNA#2 of circRNA-MYLK on those factors above. The circRNA-MYLK had oncogenic roles via targeting miR-145-5p in the Hep-2 cell line via stimulating MEK/ERK and NF-κB cascades.
Understanding soybean (Glycine max) domestication and improvement at a genetic level is important to inform future efforts to further improve a crop that provides the world's main source of oilseed. We detect 230 selective sweeps and 162 selected copy number variants by analysis of 302 resequenced wild, landrace and improved soybean accessions at >11× depth. A genome-wide association study using these new sequences reveals associations between 10 selected regions and 9 domestication or improvement traits, and identifies 13 previously uncharacterized loci for agronomic traits including oil content, plant height and pubescence form. Combined with previous quantitative trait loci (QTL) information, we find that, of the 230 selected regions, 96 correlate with reported oil QTLs and 21 contain fatty acid biosynthesis genes. Moreover, we observe that some traits and loci are associated with geographical regions, which shows that soybean populations are structured geographically. This study provides resources for genomics-enabled improvements in soybean breeding.
Gene duplication provides resources for novel gene functions. Identification of the amino acids responsible for functional conservation and divergence of duplicated genes will strengthen our understanding of their evolutionary course. Here, we conducted a systemic functional investigation of phosphatidylethanolamine binding proteins (PEBPs) in soybean (Glycine max) and Arabidopsis thaliana. Our results demonstrated that after the ancestral duplication, the lineage of the common ancestor of the FLOWERING LOCUS T (FT) and TERMINAL FLOWER1 (TFL1) subfamilies functionally diverged fromthe MOTHER OF FT AND TFL1 (MFT) subfamily to activate flowering and repress flowering, respectively. They also underwent further specialization after subsequent duplications. Although the functional divergence increased with duplication age, we observed rapid functional divergence for a few pairs of young duplicates in soybean. Association analysis between amino acids and functional variations identified critical amino acid residues that led to functional differences in PEBP members. Using transgenic analysis, we validated a subset of these differences. We report clear experimental evidence for the functional evolution of the PEBPs in the MFT, FT, and TFL1 subfamilies, which predate the origin of angiosperms. Our results highlight the role of amino acid divergence in driving evolutionary novelty after duplication.