Novel functional carbon dot based on Angelica residue and polyethyleneimine: A super-efficient corrosion and scale inhibitor.

The stability and high-dose addition of carbon dots in corrosion and scale inhibition are obstacles to their commercial application. Herein, we report a new type of functional CDs (PEI-CDA) based on Angelica residue and polyethyleneimine (PEI), which can remarkably boost the performance of corrosion and scale inhibition, while expending the application of traditional Chinese medicine waste residue. At 303.15 K, the corrosion inhibition efficiency of PEI-CDA for carbon steel in 1.0 M HCl medium was tested by weight loss method and electrochemical method and reached over 93 %, which is significantly better than that of CDA (83 %) under the same conditions. And its corrosion inhibition efficiency can still remain stable after 15 h. The ultra-low dose (5 mg·L-1) PEI-CDA has excellent anti-corrosion protection effect on carbon steel due to its ability to form a dense and well-organized adsorption film covering on the carbon steel surface, whose adsorption includes two types of chemical and physical adsorption, and follows the Langmuir adsorption model. Furthermore, static methods display that the CaSO4 scale inhibition efficiency of PEI-CDA is up to 100 % when its dosage is 100 mg·L-1. Analysis of the generated CaSO4 scale shows that the addition of PEI-CDA causes lattice distortion, chelation, and dispersion of scale. In addition, the fluorescence spectra imply that PEI-CDA can be expected to on-line detection of its residual content in the water system. The results demonstrate that PEI-CDA possesses significant potential in green inhibitors and the comprehensive utilization of waste resources.

Nitrate removal by a novel aerobic denitrifying Pelomonas puraquae WJ1 in oligotrophic condition: Performance and carbon source metabolism.

Reducing nitrate contamination in drinking water has become a critical issue in urban water resource management. Here a novel oligotrophic aerobic denitrifying bacterium, Pelomonas puraquae WJ1, was isolated and purified from artificial lake sediments. For the first time, excellent aerobic denitrification capabilities were demonstrated. At a carbon-to­nitrogen ratio of 5.0, strain WJ1 achieved 100.0 % nitrate removal and 84.92 % total nitrogen removal within 24 h, with no nitrite accumulation. PCR amplification and sequencing confirmed the presence of the denitrification genes napA, nirS, and nosZ in the strain. The nitrogen balance demonstrated that approximately 74.95 % of the initial nitrogen was eliminated as gaseous products under aerobic conditions. Furthermore, carbon balance analysis showed that most electron donors from strain WJ1 were directed towards oxygen, with limited availability for nitrate reduction. A combination of bio-ECO analysis and network modeling indicated that strain WJ1 has robust metabolic capabilities for diverse carbon sources and exhibits high adaptability to complex carbon environments. Overall, Pelomonas puraquae WJ1 removed approximately 45.89 % of the nitrates in raw water, demonstrating significant potential for practical applications in oligotrophic denitrification.

Enhanced inactivation of Aspergillus niger biofilms by the combination of UV-LEDs with chlorine-based disinfectants.

The presence of pathogenic fungal biofilms in drinking water distribution systems poses significant challenges in maintaining the safety of drinking water. This research delved into the formation of Aspergillus niger (A. niger) biofilms and evaluated their susceptibility to inactivation using combinations of ultraviolet light emitting diodes (UV-LEDs) with chlorine-based disinfectants, including UV-LEDs/chlorine (Cl2), UV-LEDs/chlorine dioxide (ClO2), and UV-LEDs/chloramine (NH2Cl) at 265 nm, 280 nm and 265/280 nm. Results indicated that A. niger biofilms reached initial maturity within 24 h, with matured three-dimensional filamentous structures and conidiospores by 96 h. UV-LEDs combined with chlorine-based disinfectants enhanced A. niger biofilm inactivation compared to UV-LEDs alone and low-pressure UV combined with chlorine-based disinfectants. At an UV fluence of 400 mJ/cm2, log reductions of UV265, UV280, and UV265/280 combined with chlorine-based disinfectants were 2.95-fold, 3.20-fold, and 2.38-fold higher than that of UV265, UV280, and UV265/280, respectively. During the inactivation, A. niger biofilm cells experienced increased membrane permeability and intracellular reactive oxygen species levels, resulting in cellular apoptosis. Extracellular polymeric substances contributed to the higher resistance of biofilms. Regarding electrical energy consumption, the order was: UV-LEDs/ClO2 > UV-LEDs/NH2Cl > UV-LEDs/Cl2. These findings provide insights into the effective utilization of UV-LEDs for fungal biofilm disinfection.

Hydrogen generated by electrochemical water splitting as electron donor for nitrate removal from micro-polluted reservoir water.

Extremely limited organic carbon sources and aerobic environment in micro-polluted reservoir water make conventional denitrification exceptionally challenging. As a result, total nitrogen (TN) concentration in most reservoir waters exceeds standard value year-round. In this study, for the first time, we constructed a mini water-lifting and aeration system (mini-WLAS) to remove nitrate in actual reservoir water. In the mini-WLAS, H2 was produced through electrolysis of reservoir water without adding any electrolyte, and the ascending water flow carried the generated H2 from lower layer to upper bacteria layer. The maximum denitrification rate reached 0.29 mg (L·d)-1 under dissolved oxygen (DO) concentration of 6-8 mg L-1, 6.04 times higher than that of the control group. There is almost no accumulation of NH4+-N, NO2--N, and N2O, and the concentration of CODMn decreased by 55.2 %. More importantly, the pH stayed near-neutral steadily throughout the whole process. Microbial community analysis showed that the abundances of hydrogenotrophic denitrifying bacteria (HDB) were 2 orders higher than those in the control system. Some HDB could work under aerobic conditions, providing an explanation for the excellent denitrification performance under high DO. This study provides a novel perspective for TN removal from reservoir water.

Spatial and temporal dynamics of microbes and genes in drinking water reservoirs: Distribution and potential for taste and odor generation.

Numerous reservoirs encounter challenges related to taste and odor issues, often attributed to odorous compounds such as geosmin (GSM) and 2-methylisoborneol (2-MIB). In this study, two large reservoirs located in northern and southern China were investigated. The Jinpen (JP) reservoir had 45.99 % Actinomycetes and 14.82 % Cyanobacteria, while the Xikeng (XK) reservoir contained 37.55 % Actinomycetes and 48.27 % Cyanobacteria. Most of the 2-MIB produced in surface layers of the two reservoirs in summer originated from Cyanobacteria, most of the 2-MIB produced in winter and in the bottom water originated from Actinomycetes. Mic gene abundance in the XK reservoir reached 5.42 × 104 copies/L in winter. The abundance of GSM synthase was notably high in the bottom layer and sediment of both reservoirs, while 2-MIB synthase was abundant in the surface layer of the XK reservoir, echoing the patterns observed in mic gene abundance. The abundance of odor-producing enzymes in the two reservoirs was inhibited by total nitrogen, temperature significantly influenced Actinomycetes abundance in the JP reservoir, whereas dissolved oxygen had a greater impact in the XK reservoir. Overall, this study elucidates the molecular mechanisms underlying odor compounding, providing essential guidance for water quality management strategies and the improvement of urban water reservoir quality.

Ignored microbial-induced taste and odor in drinking water reservoirs: Novel insight into actinobacterial community structure, assembly, and odor-producing potential.

The presence of actinobacteria in reservoirs can lead to taste and odor issues, posing potential risks to the safety of drinking water supply. However, the response of actinobacterial communities to environmental factors in drinking water reservoirs remains largely unexplored. To address this gap, this study investigated the community structure and metabolic characteristics of odor-producing actinobacteria in water reservoirs across northern and southern China. The findings revealed differences in the actinobacterial composition across the reservoirs, with Mycobacterium sp. and Candidatus Nanopelagicus being the most prevalent genera. Notably, water temperature, nutrient levels, and metal concentrations were associated with differences in actinobacterial communities, with stochastic processes playing a major role in shaping the community assembly. In addition, three strains of odor-producing actinobacteria were cultured in raw reservoir water, namely Streptomyces antibioticus LJH21, Streptomyces sp. ZEU13, and Streptomyces sp. PQK19, with peak ATP concentrations of 51 nmol/L, 66 nmol/L, and 70 nmol/L, respectively, indicating that odor-producing actinobacteria could remain metabolically active under poor nutrient pressure. Additionally, Streptomyces antibioticus LJH21 produced the highest concentration of geosmin at 24.4 ng/L. These findings enhance our understanding of regional variances and reproductive metabolic mechanisms of actinobacteria in drinking water reservoirs, providing a solid foundation for improving drinking water quality control, especially for taste and odor.

Microbial enhanced manganese-autotrophic denitrification in reactor: performance, microbial diversity, potential functions.

Autotrophic denitrification technology has gained increasing attention in recent years owing to its effectiveness, economical, and environmentally friendly nature. However, the sluggish reaction rate has emerged as the primary impediment to its widespread application. Herein, a bio-enhanced autotrophic denitrification reactor with modified loofah sponge (LS) immobilized microorganisms was established to achieve efficient denitrification. Under autotrophic conditions, a nitrate removal efficiency of 59.55 % (0.642 mg/L/h) and a manganese removal efficiency of 86.48 % were achieved after bio-enhance, which increased by 20.92 % and 36.34 %. The bioreactor achieved optimal performance with denitrification and manganese removal efficiencies of 99.84 % (1.09 mg/L/h) and 91.88 %. ETSA and 3D-EEM analysis reveled manganese promoting electron transfer and metabolic activity of microorganisms. High-throughput sequencing results revealed as the increase of Mn(II) concentration, Cupriavidus became one of the dominant strains in the reactor. Prediction of metabolic functions results proved the great potential for Mn(II)-autotrophic denitrification of LS bioreactor.

Biogeochemical cycles of iron: Processes, mechanisms, and environmental implications.

The iron (Fe) biogeochemical cycle is critical for abiotic and biological environmental processes that overlap spatially and may compete with each other. The development of modern molecular biology technologies promoted the understanding of the electron transport mechanisms of Fe-cycling-related microorganisms. Recent studies have revealed a novel pathway for microaerophilic ferrous iron (Fe(II))-oxidizers in extracellular Fe(II) oxidation. In addition, OmcS, OmcZ, and OmcE nanowires on the cell surface have been shown to promote electron transfer between microorganisms and their environment. These processes affect the fate of pollutants in directly or indirectly ways, such as greenhouse gas emissions. In this review, these advances and the environmental implications of the Fe cycle process were discussed, with a particular focus on the mechanisms of intracellular or extracellular electron transport in microorganisms.

Effects of storm events on nutrient characteristics in a stratified drinking water reservoir: Behavior, transmission pathways and management strategy.

Storm events result in nutrient fluctuations and deterioration of reservoir water supply quality. Understanding of nutrient dynamics (e.g., concentration, composition, loads and transport pathways) and adoption of effective management strategies are critical for safeguarding water quality. A comprehensive monitoring was conducted for three storm events during the rainy season in 2023. Results showed nitrogen (N) and phosphorus (P) dynamics demonstrate a significant response to hydrological process. Rainfall resulted in the highest event mean concentrations (EMCs) of total nitrogen (TN), nitrate nitrogen (NO3--N), ammonia nitrogen (NH4+-N), total phosphorus (TP), and particulate phosphorus (PP) in the runoff being 1.97, 2.15, 2.30, 44.17, and 62.38 times higher than those observed in baseflow. On average, NO3--N/PP accounted for 82 %/96 % of N/P exports. Hysteresis analyses reveal that NH4+-N and PP were mainly transported by surface runoff from over-land sources, whereas TN and NO3--N were primarily delivered by subsurface runoff. Additionally, nutrient concentrations were significantly higher in the intrusive layer in reservoir compared to the pre-storm period, which gradually decreased from the tail to the head as particulate sedimentation and water column mixing occurred. Water-lifting-aerators (WLAs) were employed to alter the reservoir thermal stratification regime via artificial mixing to affect the intrusive layer of storm runoff. Comparison of the intrusive layer for three storms reveals that WLAs triggers the storm runoff to form an underflow via increasing the reservoir bottom water temperature above that the runoff, ensuring that water quality at the intake position remains unaffected by inflows. These findings serve as a reference for the response of reservoir eutrophication levels to storm events and present practical engineering experience for enhancing water quality safety during the rainy season.

Aerobic denitrifying bacterial community with low C/N ratio remove nitrate from micro-polluted water: Metagenomics unravels denitrification pathways.

The efficient nitrogen removal from micro-polluted source water is an international challenge to be solved urgently. However, the inner denitrification mechanism of native aerobic denitrifying bacterial communities in response to carbon scarcity remains relatively unclear. Here, the bacterial community XT6, screened from an oligotrophic reservoir, exhibited aerobic denitrifying capacity under low-carbon environments. Up to 76.79-81.64 % of total organic carbon (TOC) and 51.48-67.60 % of NO3--N were removed by XT6 within 48 h at C/N ratios of 2.0-3.0. Additionally, the nitrogen balance experiments further manifested that 26.27-38.13 % of NO3--N was lost in gaseous form. As the C/N ratio decreased, XT6 tended to generate more extracellular polymeric substances (EPS), with the tightly bound EPS showing the largest increase. Pseudomonas and Variovorax were quite abundant in XT6, constituting 59.69 % and 28.65 % of the total sequences, respectively. Furthermore, metagenomics analysis evidenced that XT6 removed TOC and nitrate mainly through the tricarboxylic acid cycle and aerobic denitrification. Overall, the abovementioned results provide a deeper understanding of the nitrogen metabolic pathways of indigenous aerobic denitrifying bacterial communities with low C/N ratios and offer useful guidance for controlling nitrogen pollution in oligotrophic ecosystems.

Emergency control of dinoflagellate bloom in freshwater with chlorine enhanced by solar radiation: Efficiency and mechanism.

Dinoflagellate requires a lower temperature and blooms frequently in the spring and autumn compared to regular cyanobacteria. The outbreak of dinoflagellate bloom will also lead to the death of some aquatic organisms. However, research on freshwater dinoflagellates is still lacking due to the challenges posed by classification and culture in laboratory. The removal effect and mechanism of Peridinium umbonatum (P. umbonatum, a typical dinoflagellate) were investigated using solar/chlorine in this study. The effect of simulated solar alone on the removal of algae was negligible, and chlorine alone had only a slight effect in removing algae. However, solar/chlorine showed a better removal efficiency with shoulder length reduction factor and kmax enhancement factor of 2.80 and 3.8, respectively, indicating a shorter latency period and faster inactivation rate for solar/chlorine compared to solar and chlorine alone. The removal efficiency of algae gradually increased with the chlorine dosage, but it dropped as the cell density grew. When the experimental temperature was raised to 30 °C, algal removal efficiency significantly increased, as the temperature was unsuitable for the survival of P. umbonatum. Attacks on cell membranes by chlorine and hydroxyl radicals (•OH) produced by solar/chlorine led to a decrease in cell membrane integrity, leading to a rise in intracellular reactive oxygen species and an inhibition of photosynthetic and antioxidant systems. Cell regeneration was not observed in either the chlorine or solar/chlorine systems due to severe cell damage or cysts formation. In addition, natural solar radiation was demonstrated to have the same enhancing effect as simulated solar radiation. However, the algal removal efficiency of solar/chlorine in real water was reduced compared to 119 medium, mainly due to background material in the real water substrate that consumed the oxidant or acted as shading agents.

Solar/ClO2 system inactivates fungal spores in drinking water: Synergy, efficiency and mechanisms.

The risk of fungal pollution in drinking water has been paid attention. Solar/chlorine dioxide (ClO2) combined system is an environment-friendly, economical and efficient disinfection method, especially for countries and regions that are economically backward and still exposed to unsafe drinking water. In this paper, the kinetics, influencing factors, mechanism and regrowth potential of inactivated Aspergillus niger (A. niger) spores by solar/ClO2 were reported for the first time. The inactivation curve can be divided into three stages: instant inactivation within 1-2 min, slow linear inactivation and finally a tail. The synergistic factors produced by solar/ClO2 in terms of log reduction and maximum inactivation rate were 1.194 and 1.112, respectively. The inhibitory effect on the regrowth of A. niger spores inactivated by solar/ClO2 was also stronger than that by ClO2 alone. Strongly oxidizing reactive species produced by solar/ClO2 accelerated the accumulation of endogenic reactive oxygen species (ROS) caused by oxidation stress of A. niger spores, improving the inactivation ability of the system. The inactivation order of A. niger spores was: loss of culturability, accumulation of intracellular ROS, loss of membrane integrity, leakage of intracellular species and change of morphology. The inactivation performance of solar/ClO2 was better than solar/chlor(am)ine according to the comparison of inactivation efficiency and regrowth potential. Results also suggested that solar/ClO2 process was more suitable for the treatment of ground water sources.

Microbial-induced calcium precipitation: Bibliometric analysis, reaction mechanisms, mineralization types, and perspectives.

Microbial-induced calcium precipitation (MICP) refers to the formation of calcium precipitates induced by mineralization during microbial metabolism. MICP has been widely used as an ecologically sustainable method in environmental, geotechnical, and construction fields. This article reviews the removal mechanisms of MICP for different contaminants in the field of water treatment. The nucleation pathway is explained at both extracellular and intracellular levels, with a focus on evaluating the contribution of extracellular polymers to MICP. The types of mineralization and the regulatory role of enzyme genes in the MICP process are innovatively summarized. Based on this, the environmental significance of MICP is illustrated, and the application prospects of calcium precipitation products are discussed. The research hotspots and development trends of MICP are analyzed by bibliometric methods, and the challenges and future directions of MICP technology are identified. This review aims to provide a theoretical basis for further understanding of the MICP phenomenon in water treatment and the effective removal of multiple pollutants, which will help researchers to find the breakthroughs and innovations in the existing technologies, with a view to making significant progress in MICP technology.

Response of the algal-bacterial community to thermal stratification succession in a deep-water reservoir: Community structure, co-assembly patterns, and functional groups.

Thermal stratification in lakes and reservoirs may intensify and become more persistent with global warming. Periodic thermal stratification is a naturally occurring phenomenon that indicates a transition in aquatic ecosystem homeostasis, which could lead to the deterioration of water quality and impaired aquatic communities. However, the responses of communities and associated nutrient cycling processes to periodic thermal stratification are still poorly understood. This study delved into the changes in water quality, algal-bacterial communities, and functional diversity influenced by thermal stratification succession, and their relationship with nutrient cycling. The results indicated that the apparent community dynamics were driven by environmental factors, with ammonium (NH4+) and nitrate (NO3--N) being the most important factors that influenced the algal and bacterial community structure, respectively. Ecological niche widths were narrower during thermal stratification, exacerbating the antagonism of the communities, and stochastic processes dominated community assembly. Then, the complexities of the co-occurrence network decreased with succession. Algal community assembly became more deterministic, while bacterial assembly became more stochastic. Moreover, the roles of algal-bacterial multidiversity in nutrient cycling differed: bacterial diversity enhanced nutrient cycling, whereas algal diversity had the opposite effect. These findings broadened our understanding of microbial ecological mechanisms to environmental change and provided valuable ecological knowledge for securing water supplies in drinking water reservoirs.

Disentangling the assembly patterns and drivers of microbial communities during thermal stratification and mixed periods in a deep-water reservoir.

Effect of periodic thermal stratification in deep-water reservoirs on aquatic ecosystems has been a research hotspot. Nevertheless, there is limited information on the response patterns of microbial communities to environmental changes under such specialized conditions. To fill this gap, samples were collected from a typical deep-water reservoir during the thermal stratification period (SP) and mixed period (MP). Three crucial questions were answered: 1) How microbial communities develop with stratified to mixed succession, 2) how the relative importance of stochastic and deterministic processes to microbial community assembly, shifted in two periods, and 3) how environmental variables drive microbial co-occurrence networks and functional group alteration. We used Illumina Miseq high-throughput sequencing to investigate the dynamics of the microbial community over two periods, constructed molecular ecological networks (MENs), and unraveled assembly processes based on null and neutral models. The results indicated that a total of 33.9 % and 27.7 % of bacterial taxa, and 23.1 % and 19.4 % of fungal taxa were enriched in the stratified and mixed periods, respectively. Nitrate, water temperature, and total phosphorus drove the variation of microbial community structure. During the thermal stratification period, stochastic processes (dispersal limitation) and deterministic processes (variable selection) dominated the assembly of bacterial and fungal communities, followed by a shift to stochastic processes dominated by dispersal limitation in two communities. The MENs results revealed that thermal stratification-induced environmental stresses increased the complexity of microbial networks but decreased its robustness, resulting in more vulnerable ecological networks. Therefore, this work provides critical ecological insights for the longevity and sustainability of water quality management in an artificially regulated engineered system.

Ammonium nitrogen and phosphorus removal by bacterial-algal symbiotic dynamic sponge bioremediation system in micropolluted water: Operational mechanism and transformation pathways.

Construct a bacteria-algae symbiotic dynamic sponge bioremediation system to simultaneously remove multiple pollutants under micro-pollution conditions. The average removal efficiencies of NH4+-N, PO43--P, total nitrogen (TN), and Ca2+ were 98.35, 78.74, 95.64, and 84.92 %, respectively. Comparative studies with Auxenochlorella sp. sponge and bacterial sponge bioremediation system confirmed that NH4+-N and TN were mainly removed by bacterial heterotrophic nitrification - aerobic denitrification (HN-AD). PO43--P was removed by algal assimilation and the generation of Ca3(PO4)2 and Ca5(PO4)3OH, and Ca2+ was removed by algal electron transfer formation of precipitates and microbially induced calcium precipitation (MICP) by bacteria. Algae provided an aerobic environment for the bacterial HN-AD process through photosynthesis, while respiration produced CO2 and adsorbed Ca2+ to promote the formation of calcium precipitates. Immobilization of Ca2+ with microalgae via bacterial MICP helped to lift microalgal photoinhibition. The bioremediation system provides theoretical support for research on micropolluted water treatment while increasing phosphorus recovery pathways.

Formation of filamentous fungal biofilms in water and the transformation of resistance to chlor(am)ine disinfection.

Biofilms are composed of complex multi-species in nature, potentially threatening drinking water safety. In this work, the formation of single- and multi-species fungal biofilms formed by Aspergillus niger (A. niger) and Aspergillus flavus (A. flavus), and the inactivation of mature biofilms using chlor(am)ine were firstly investigated. Results revealed that the antagonistic interaction occurred between A. niger and A. flavus. Chloramination at 20 mg/L for 30 min achieved 74.74 % and 76.04 % inactivation of A. flavus and multi-species biofilm, which were 1.69- and 1.84-fold higher than that of chlorine at the same condition. However, no significant difference was observed in the inactivation of A. niger biofilm between chlorine and monochloramine disinfection due to the lower amount of extracellular polymeric substance produced by it (p > 0.05). The inactivation of biofilm by monochloramine fitted the Weibull model well. According to the Weibull model, the monochloramine resistance of biofilm were as follows: A. flavus > multi-species > A. niger biofilm. Besides, an increase in reactive oxygen levels, damage of cell membrane, and leakage of intracellular substances in biofilms were observed after chlor(am)ination. More intracellular polysaccharides and proteins were leaked in chloramination inactivation (p < 0.05). This study provides important implications for controlling fungal biofilm.

Mixotrophic aerobic denitrification facilitated by denitrifying bacterial-fungal communities assisted with iron in micro-polluted water: Performance, metabolic activity, functional genes abundance, and community co-occurrence.

Low-dosage nitrate pollutants can contribute to eutrophication in surface water bodies, such as lakes and reservoirs. This study employed assembled denitrifying bacterial-fungal communities as bio-denitrifiers, in combination with zero-valent iron (ZVI), to treat micro-polluted water. Immobilized bacterial-fungal mixed communities (IBFMC) reactors demonstrated their ability to reduce nitrate and organic carbon by over 43.2 % and 53.7 %, respectively. Compared to IBFMC reactors, IBFMC combined with ZVI (IBFMC@ZVI) reactors exhibited enhanced removal efficiencies for nitrate and organic carbon, reaching the highest of 31.55 % and 17.66 %, respectively. The presence of ZVI in the IBFMC@ZVI reactors stimulated various aspects of microbial activity, including the metabolic processes, electron transfer system activities, abundance of functional genes and enzymes, and diversity and richness of microbial communities. The contents of adenosine triphosphate and electron transfer system activities enhanced more than 5.6 and 1.43 folds in the IBFMC@ZVI reactors compared with IBFMC reactors. Furthermore, significant improvement of crucial genes and enzyme denitrification chains was observed in the IBFMC@ZVI reactors. Iron played a central role in enhancing microbial diversity and activity, and promoting the supply, and transfer of inorganic electron donors. This study presents an innovative approach for applying denitrifying bacterial-fungal communities combined with iron enhancing efficient denitrification in micro-polluted water.

Comparing Mn-based oxides filters started by KMnO4 versus K2FeO4 for ammonium and manganese removal: Formation mechanism of active species.

A pilot-scale filtration system was adopted to prepare filter media with catalytic activity to remove manganese (Mn2+) and ammonium (NH4+-N). Three different combinations of oxidants (KMnO4 and K2FeO4) and reductants (MnSO4 and FeCl2) were used during the start-up period. Filter R3 started up by KMnO4 and FeCl2 (Mn7+→MnOx) exhibited excellent catalytic property, and the NH4+-N and Mn2+ removal efficiency reached over 80% on the 10th and 35th days, respectively. Filter R1 started up by K2FeO4 and MnSO4 (MnOx←Mn2+) exhibited the worst catalytic property. Filter R2 started up by KMnO4 and MnSO4 (Mn7+→MnOx←Mn2+) were in between. According to Zeta potential results, the Mn-based oxides (MnOx) formed by Mn7+→MnOx performed the highest pHIEP and pHPZC. The higher the pHIEP and pHPZC, the more unfavorable the cation adsorption. However, it was inconsistent with its excellent Mn2+ and NH4+-N removal abilities, implying that catalytic oxidation played a key role. Combined with XRD and XPS analysis, the results showed that the MnOx produced by the reduction of KMnO4 showed early formation of buserite crystals, high degree of amorphous, high content of Mn3+ and lattice oxygen with the higher activity to form defects. The above results showed that MnOx produced by the reduction of KMnO4 was more conducive to the formation of active species for catalytic oxidation of NH4+-N and Mn2+ removal. This study provides new insights on the formation mechanisms of the active MnOx that could catalytic oxidation of NH4+-N and Mn2+.

Molecular-level insight into the behavior of metal cations and organic matter during the aggregation of polystyrene nanoplastics.

In this study, the behavior of metal cations and organic matter during polystyrene nanoplastics (PSNP) aggregation was explored combing experimental measurements and molecular dynamics simulation. The results indicated that coexisting organic matter, including organic pollutants and humic acid (HA), play a complex role in determining PSNP aggregation. The representative organic pollutant, bisphenol A, exhibited competitive behavior with HA during heteroaggregation, and the heteroaggregation between HA and PSNP was impaired by bisphenol A. The bridging effect of metal ions in aggregation is related to their interaction strength with functional groups, binding affinity with water molecules, and concentration. In particular, Mg2+ interacts more strongly with oxygen-containing functional groups on PSNP than Ca2+. However, Mg2+ is more favorable for binding with water and is therefore not as effective as Ca2+ for destabilizing PSNP. Compared with Ca2+ and Mg2+, Na+ showed a weaker association with PSNP; however, it still showed a significant effect in determining the aggregation behavior of PSNP owing to its high concentration in seawater. Overall, we provided a molecular-level understanding of PSNP aggregation and deepened our understanding of the fate of nanoplastics.