Toxic effects of nanoplastics on biological nitrogen removal in constructed wetlands: Evidence from iron utilization and metabolism.

Nanoplastics (NPs) in wastewaters may present a potential threat to biological nitrogen removal in constructed wetlands (CWs). Iron ions are pivotal in microbially mediated nitrogen metabolism, however, explicit evidence demonstrating the impact of NPs on nitrogen removal regulated by iron utilization and metabolism remains unclear. Here, we investigated how NPs disturb intracellular iron homeostasis, consequently interfering with the coupling mechanism between iron utilization and nitrogen metabolism in CWs. Results indicated that microorganisms affected by NPs developed a siderophore-mediated iron acquisition mechanism to compensate for iron loss. This deficiency resulted from NPs internalization limited the activity of the electron transport system and key enzymes involved in nitrogen metabolism. Microbial network analysis further suggested that NPs exposure could potentially trigger destabilization in microbial networks and impair effective microbial communication, and ultimately inhibit nitrogen metabolism. These adverse effects, accompanied by the dominance of Fe3+ over certain electron acceptors engaged in nitrogen metabolism under NPs exposure, were potentially responsible for the observed significant deterioration in nitrogen removal (decreased by 30 %). This study sheds light on the potential impact of NPs on intracellular iron utilization and offers a substantial understanding of the iron-nitrogen coupling mechanisms in CWs.

Characteristics and mechanisms of phosphine production in sulfur-based constructed wetlands.

Phosphine (PH3) is an important contributor to the phosphorus cycle and is widespread in various environments. However, there are few studies on PH3 in constructed wetlands (CWs). In this study, lab-scale CWs and batch experiments were conducted to explore the characteristics and mechanisms of PH3 production in sulfur-based CWs. The results showed that the PH3 release flux of sulfur-based CWs varied from 0.86±0.04 ng·m-2·h-1 to 1.88±0.09 ng·m-2·h-1. The dissolved PH3 was the main PH3 form in CWs and varied from 2.73 µg·L-1 to 4.08 µg·L-1. The matrix-bound PH3 was a staging reservoir for PH3 and increased with substrate depth. In addition, the sulfur-based substrates had a significant improvement on PH3 production. Elemental sulfur is more conducive to PH3 production than pyrite. Moreover, there was a significant positive correlation between PH3 production, the dsrB gene, and nicotinamide adenine dinucleotide (NADH). NADH might catalyze the phosphate reduction process. And the final stage of the dissimilatory sulfate reduction pathway driven by the dsrB gene might also provide energy for phosphate reduction. The migration and transformation of PH3 increased the available P (Resin-P and NaHCO3-P) from 35 % to 56 % in sulfur-based CW, and the P adsorption capacity was improved by 12 %. The higher proportion of available P increased the plant uptake rate of P by 17 %. This study improves the understanding of the phosphorus cycle in sulfur-based CW and provides new insight into the long-term stable operation of CWs.

Two synonymous single-nucleotide polymorphisms promoting fluoroquinolone resistance of Escherichia coli in the environment.

Single-nucleotide polymorphism (SNP) is one of the core mechanisms that respond to antibiotic resistance of Escherichia coli (E. coli), which is a major issue in environmental pollution. A specific type of SNPs, synonymous SNPs, have been generally considered as the "silent" SNPs since they do not change the encoded amino acid. However, the impact of synonymous SNPs on mRNA splicing, nucleo-cytoplasmic export, stability, and translation was gradually discovered in the last decades. Figuring out the mechanism of synonymous SNPs in regulating antibiotic resistance is critical to improve antimicrobial therapy strategies in clinics and biological treatment strategies of antibiotic-resistant E. coli-polluted materials. With our newly designed antibiotic resistant SNPs prediction algorithm, Multilocus Sequence Type based Identification for Phenotype-single nucleotide polymorphism Analysis (MIPHA), and in vivo validation, we identified 2 important synonymous SNPs 522 G>A and 972 C>T, located at hisD gene, which was previously predicted as a fluoroquinolone resistance-related gene without a detailed mechanism in the E. coli samples with environmental backgrounds. We first discovered that hisD causes gyrA mutation via the upregulation of sbmC and its downstream gene umuD. Moreover, those 2 synonymous SNPs of hisD cause its own translational slowdown and further reduce the expression levels of sbmC and its downstream gene umuD, making the fluoroquinolone resistance determining region of gyrA remains unmutated, ultimately causing the bacteria to lose their ability to resist drugs. This study provided valuable insight into the role of synonymous SNPs in mediating antibiotic resistance of bacteria and a new perspective for the treatment of environmental pollution caused by drug-resistant bacteria.

Investigation on the role of ·OH for BPA removal in coastal sediments: The important mediation of low reactivity Fe(II).

Bisphenol A (BPA) in seawater tends to be deposited in coastal sediments. However, its degradation under tidal oscillations has not been explored comprehensively. Hydroxyl radicals (·OH) can be generated through Fe cycling under redox oscillations, which have a strong oxidizing capacity. This study focused on the contribution of Fe-mediated production of ·OH in BPA degradation under darkness. The removal of BPA was investigated by reoxygenating six natural coastal sediments, and three redox cycles were applied to prove the sustainability of the process. The importance of low reactivity Fe(II) in the production of ·OH was investigated, specifically, Fe(II) with carbonate and Fe(II) within goethite, hematite and magnetite. The degradation efficiency of BPA during reoxygenation of sediments was 76.78-94.82%, and the contribution of ·OH ranged from 36.74% to 74.51%. The path coefficient of ·OH on BPA degradation reached 0.6985 and the indirect effect of low reactivity Fe(II) on BPA degradation by mediating ·OH production reached 0.5240 obtained via partial least squares path modeling (PLS-PM). This study emphasizes the importance of low reactivity Fe(II) in ·OH production and provides a new perspective for the role of tidal-induced ·OH on the fate of refractory organic pollutants under darkness.

To What Extent Do Iodomethane and Bromomethane Undergo Analogous Reactions?

Iodomethane and bromomethane (CH3I/CH3Br) are common chemicals, but their chemistry on nanometals is not fully understood. Here, we analyze the reactivity of Rhn+ (n = 3-30) clusters with halomethanes and unveil the spin effect and concentration dependence in the C-H and C-X bond activation. It is found that the reactions under halomethane-rich conditions differ from those under metal-rich conditions. Both CH3I and CH3Br undergo similar dehydrogenation on the Rhn+ clusters in the presence of small quantity reactants; however, different reactions are observed in the presence of sufficient CH3I/CH3Br, showing dominant Rh(CH3Br)x+ (x = 1-4) products but a series of RhnCxHyIz+ species (x = 1-4, y = 1-12, and z = 1-5) pertaining to H2, HI, or CH4 removal. Density functional theory calculations reveal that the dehydrogenation and demethanation of CH3Br are relatively less exothermic and will be deactivated by sufficient gas collisions if helium cooling takes away energy immediately; instead, the successive adsorption of CH3Br gives rise to a series of Rh(CH3Br)x+ species with accidental C-Br bond dissociation.

Efficient stabilization of arsenic migration and conversion in soil with surfactant-modified iron-manganese oxide: Environmental effects and mechanistic insights.

The use of iron-manganese oxide (FMO) as a promising amendment for remediating arsenic (As) contamination in soils has gained attention, but its application is limited owing to agglomeration issues. This study aims to address agglomeration using surfactant-modified FMO and investigate their stabilization behavior towards As and resulting environmental changes upon amendments. The results confirmed the efficacy of surfactants and demonstrated that cetyltrimethylammonium-bromide-modified FMO significantly reduced the leaching concentration of As by 92.5 % and effectively suppressed the uptake of As by 85.8 % compared with the control groups. The ratio of the residual fraction increased from 30.5-41.6 % in unamended soil to 67.9-69.2 %. The number of active sites was through the introduction of surfactants and immobilized As via complexation, ion exchange, and redox reactions. The study also revealed that amendments and the concentration of As influenced the soil physicochemical properties and enriched bacteria associated with As and Fe reduction and changed the distribution of C, N, Fe, and As metabolism genes, which promoted the stabilization of As. The interactions among cetyltrimethylammonium bromide, FMO, and microorganisms were found to have the greatest effect on As immobilization.

Differential Nitrous oxide emission and microbiota succession in constructed wetlands induced by nitrogen forms.

Nitrous oxide (N2O) emission during the sewage treatment process is a serious environmental issue that requires attention. However, the N2O emission in constructed wetlands (CWs) as affected by different nitrogen forms in influents remain largely unknown. This study investigated the N2O emission profiles driven by microorganisms in CWs when exposed to two typical nitrogen sources (NH4+-N or NO3--N) along with different carbon source supply (COD/N ratios: 3, 6, and 9). The results showed that CWs receiving NO3--N caused a slight increase in total nitrogen removal (by up to 11.8 %). This increase was accomplished by an enrichment of key bacteria groups, including denitrifiers, dissimilatory nitrate reducers, and assimilatory nitrate reducers, which enhanced the stability of microbial interaction. Additionally, it led to a greater abundance of denitrification genes (e.g., nirK, norB, norC, and nosZ) as inferred from the database. Consequently, this led to a gradual increase in N2O emission from 66.51 to 486.77 ug-N/(m2·h) as the COD/N ratio increased in CWs. Conversely, in CWs receiving NH4+-N, an increasing influent COD/N ratio had a negative impact on nitrogen biotransformation. This resulted in fluctuating trend of N2O emissions, which decreased initially, followed by an increase at later stage (with values of 122.87, 44.00, and 148.59 ug-N/(m2·h)). Furthermore, NH4+-N in the aquatic improved the nitrogen uptake by plants and promoted the production of more root exudates. As a result, it adjusted the nitrogen-transforming function, ultimately reducing N2O emissions in CWs. This study highlights the divergence in microbiota succession and nitrogen transformation in CWs induced by nitrogen form and COD/N ratio, contributing to a better understanding of the microbial mechanisms of N2O emission in CWs with NH4+-N or NO3--N at different COD/N ratios.

The critical role of microplastics in the fate and transformation of sulfamethoxazole and antibiotic resistance genes within vertical subsurface-flow constructed wetlands.

Constructed wetlands (CWs) are reservoirs of microplastics (MPs) in the environment. However, knowledge about the impact of MPs on antibiotic removal and the fate of antibiotic resistance genes (ARGs) is limited. We focused on sulfamethoxazole (SMX) as a representative compound to examine the effects of MPs on SMX removal and the proliferation and dissemination of two SMX-related ARGs (sul1 and sul2) in vertical subsurface-flow CW (VFCW) microcosm. The presence of MPs in the substrate was found to enhance the proliferation of microorganisms owing to the large specific surface area of the MPs and the release of dissolved organic carbon (DOC) on MP surfaces, which resulted in a high SMX removal ranging from 97.80 % to 99.80 %. However, the presence of MPs promoted microbial interactions and the horizontal gene transfer (HGT) of ARGs, which led to a significant increase in the abundances of sul1 and sul2 of 68.47 % and 17.20 %, respectively. It is thus imperative to implement rigorous monitoring strategies for MPs to mitigate their potential ecological hazards.

Releasing and Assessing the Toxicity of Polycyclic Aromatic Hydrocarbons from Biochar Loaded with Iron.

Iron (Fe)-loaded biochar has garnered attention for its potential applications in recent years. However, the pyrolysis process of Fe-loaded biochar generates polycyclic aromatic hydrocarbons (PAHs), which can have adverse effects on both human health and the environment. This study explored the correlation between Fe loading and PAH production in Fe-loaded biochar. The results indicate that increasing Fe loading in biochar reduces the PAH concentration, with the most significant decrease observed in naphthalene (0.02-0.08 mg/kg). This reduction can be attributed to the decrease in precursor compounds (e.g., C2H2), substitution of the C=O bond by Fe-O, and a decrease in the dissolved organic matter concentration (3.19-10.76 mg/L) with Fe loading. When Fe loading increased from 0 to 10%, the ecological toxicity of biochar increased by 33.48% due to an elevated production of dibenzo[a,h]anthracene, which poses a significant risk to human health. Therefore, it is imperative to take into consideration the ecological risk of PAHs prior to the application of Fe-loaded biochar. This study presents a comprehensive risk assessment of Fe-loaded biochar and provides valuable insights into the optimization of its production and safe application.

Mechanism and dynamics of Baeyer-Villiger oxidation of furfural to maleic anhydride in presence of H2O2 and Au clusters.

CONTEXT: The increasing demand for fuels and chemicals in the world has prompted the exploration of various forms of renewable energy resources. Using C5-based furfural as the platform to replace the fossil energy resources is greatly attractive because of its abundance and environmental friendliness. Here we study the activity, selectivity, and possible reaction pathways for the Baeyer-Villiger oxidation of furfural over small Au clusters using hydrogen peroxide as oxidant. Furfural reacts with hydrogen peroxide in the presence of the catalysts with 93% selectivity towards maleic anhydride. Natural population analysis, frontier molecular orbital analysis, and spectroscopic analysis are used to illustrate the interaction mechanism between C5H4O2, H2O2, and Au. Reaction pathways leading to the formation of maleic anhydride are also explored. The reaction of C5H4O2 with H2O2 in the absence of a catalyst bears a relatively high transition state energy barrier of 2.98 eV for the first step involving absorption of H atom of H2O2 on the -OH group of C5H4O2. This is in agreement with the blank experiment where there were rare oxidation products observed in the absence of the metal cluster catalysts. On the other hand, transition state energies in the presence of the Au metal clusters are lower and the most feasible pathway is where the substrate and H2O2 co-bind on the Au catalyst and H2O2 molecule transfers an oxygen to the substrate, leading to the cleavage of the O-O bond. METHODS: DFT calculations were done with B3PW91 functional. 6-311G(df, p) basis set was used for C, O, and H and aug-cc-pVDZ-PP was used for gold atoms. Gaussian 09 software was used for the calculations. Multiwfn 3.7 dev was used for the quantum theory of atoms-in-molecules (QTAIM) investigations.

Plant development alters the nitrogen cycle in subsurface flow constructed wetlands: Implications to the strategies for intensified treatment performance.

Plant development greatly influences the composition structure and functions of microbial community in constructed wetlands (CWs) via plant root activities. However, our knowledge of the effect of plant development on microbial nitrogen (N) cycle is poorly understood. Here, we investigated the N removal performance and microbial structure in subsurface flow CWs at three time points corresponding to distinct stages of plant development: seedling, mature and wilting. Overall, the water parameters were profoundly affected by plant development with the increased root activities including radial oxygen loss (ROL) and root exudates (REs). The removal efficiency of NH4+-N was significantly highest at the mature stage (p < 0.01), while the removal performance of NO3--N at the seedling stage. The highest relative abundances of nitrification- and anammox-related microbes (Nitrospira, Nitrosomonas, and Candidatus Brocadia, etc.) and functional genes (Amo, Hdh, and Hzs) were observed in CWs at the mature stage, which can be attributed to the enhanced intensity of ROL, creating micro-habitat with high DO concentration. On the other hand, the highest relative abundances of denitrification- and DNRA-related microbes (Petrimonas, Geobacter, and Pseudomonas, etc.) and functional genes (Nxr, Nir, and Nar, etc.) were observed in CWs at the seedling and wilting stages, which can be explained by the absence of ROL and biological denitrification inhibitor derived from REs. Results give insights into microbial N cycle in CWs with different stages of plant development. More importantly, a potential solution for intensified N removal via the combination of practical operation and natural regulation is proposed.

Distribution, sources, ecological risk and microbial response of polycyclic aromatic hydrocarbons in Qingdao bays, China.

Bay ecosystem has garnered significant attention due to the severe threat posed by organic pollutants, particularly polycyclic aromatic hydrocarbons (PAHs). However, there is a dearth of information regarding the extent of PAHs pollutant risk and its impact on microbial communities and metabolism within this environment. In this study, the distribution, sources, ecological risk, and microbial community and metabolic response of PAHs in Jiaozhou Bay, Aoshan Bay, and Lingshan Bay in Qingdao, China were investigated. The results showed that the average concentration of ∑PAHs ranged from 120 to 614 ng/L across three bays, with Jiaozhou and Aoshan Bay exhibiting a higher risk than Lingshan Bay due to an increased concentration of high-molecular-weight PAHs. Further analysis revealed a negative correlation between dissolved organic carbon concentration and ∑PAHs concentration in water. Metagenomic analysis demonstrated that higher levels of PAHs can lead to decreased microbial diversity, while the abundance of PAHs-degrading bacteria is enhanced. Additionally, the Erythrobacter, Jannaschia and Ruegeria genera were found to have a significant correlation with low-molecular-weight PAH concentrations. In terms of microbial metabolism, higher PAH concentrations were beneficial for carbohydrate metabolic pathway but unfavorable for amino acid metabolic pathways and membrane transport pathways in natural bay environments. These findings provide a foundation for controlling PAHs pollution and offer insights into the impact of PAHs on bacterial communities and metabolism in natural bay environments.

Highly efficient phosphorous removal in constructed wetland with iron scrap: Insights into the microbial removal mechanism.

Excessive phosphorus (P) in surface water can lead to serious eutrophication and economic losses. Iron-based constructed wetland (CW) is considered as a promising solution to eliminate P effectively due to the advantage of low-cost. However, there is limited available information on the microbial removal mechanism of P in iron-based CW up to now. Therefore, CW with iron scrap was constructed to investigate the treatment performance and microbial removal mechanism in this study. Results showed that efficient and stable P removal (97.09 ± 1.90%) was achieved in iron scrap-based CW during the experiment period, which was attributed to the precipitation of iron and P and improved microbially mediated P removal. Metagenomic analysis showed that microbial diversity was enhanced and phosphate accumulating organisms (e.g., Dechloromonas and Tetrasphaera) were enriched in CW with iron scrap, which explained higher P removal reasonably. In addition, the abundance of genes involved in the P starvation (e.g., phoB), uptake and transport (e.g., pstB) were enhanced in iron scrap-based CW. Enrichment analysis demonstrated that phosphotransferase pathway was also significantly up-regulated in CW with iron scraps, indicating that the energy supply of microbial P removal was enhanced. These findings provide a better understanding of the microbial removal mechanism of P in iron-based CW.

Size-dependent promotion of micro(nano)plastics on the horizontal gene transfer of antibiotic resistance genes in constructed wetlands.

Constructed wetlands (CWs) have been identified as significant sources of micro(nano)plastics (MPs/NPs) and antibiotic resistance genes (ARGs) in aquatic environments. However, little is known about the impact of MPs/NPs exposure on horizontal gene transfer (HGT) of ARGs and shaping the corresponding ARG hosts' community. Herein, the contribution of polystyrene (PS) particles (control, 4 mm, 100 µm, and 100 nm) to ARG transfer was investigated by adding an engineered fluorescent Escherichia coli harboring RP4 plasmid-encoded ARGs into CWs. It was found MPs/NPs significantly promoted ARG transfer in a size-dependent manner in each CW medium (p < 0.05). The 100 µm-sized PS exhibited the most significant promotion of ARG transfer (p < 0.05), whereas 100 nm-sized PS induced limited promotion due to its inhibitory activity on microbes. The altered RP4-carrying bacterial communities suggested that MPs/NPs, especially 100 µm-PS, could recruit pathogenic and nitrifying bacteria to acquire ARGs. The increased sharing of RP4-carrying core bacteria in CW medium further suggested that ARGs can spread into CW microbiome using MPs/NPs as carriers. Overall, our results highlight the high risks of ARG dissemination induced by MPs/NPs exposure and emphasize the need for better control of plastic disposal to prevent the potential health threats.

Microbiota and genetic potential for reducing nitrous oxide emissions by biochar in constructed wetlands.

The denitrification process in constructed wetlands (CWs) is responsible for most of the nitrous oxide (N2O) emissions, which is an undesired impact on the ecology of sewage treatment systems. This study compared three types of CWs filled with gravel (CW-B), gravel mixed with natural pyrite (CW-BF), or biochar (CW-BC) to investigate their impact on microbiota and genetic potential for N2O generation during denitrification under varying chemical oxygen demand (COD) to nitrate (NO3--N) ratios. The results showed that natural pyrite and biochar were superior in enhancing COD (90.6-91.2 %) and NO3--N removal (90.0-93.5 %) in CWs with a COD/NO3--N ratio of 9. The accumulation of NO2--N during the denitrification process was the primary cause of N2O emission, with the fluxes ranging from 95.6-472.0 µg/(m2·h) in CW-B, 92.9-400 µg/(m2·h) in CW-BF, and 54.0-293.3 µg/(m2·h) in CW-BC. The addition of biochar significantly reduced N2O emissions during denitrification, while natural pyrite had a lesser inhibitory effect on N2O emissions. The three types of substrates also influenced the structure of microbiota in the biofilm, with natural pyrite enriched nitrogen transformation microorganisms, especially for denitrifiers. Notably, biochar significantly enhanced the abundance of nosZ and the ratio of nosZ/(norB + norC), which are critical factors in reducing N2O emissions from CWs. Overall, the results suggest that the biochar-induced changes in microbiota and genetic potential during denitrification play a significant role in preventing N2O production in CWs, especially when treating sewage with a relatively high COD/NO3--N ratio.

Chromium removal at neutral pHs via electrochemical Cr(VI) reduction and subsequent Cr(III) adsorption with MoS2 nanoflowers-modified graphite felt.

The operation performance and stability of electrochemical Cr(VI) reduction are strongly restricted at neutral pHs (e.g., drinking water and groundwater) by the high Cr(VI) oxidation potentials and cathode passivation of Cr(OH)3 precipitates. Herein, we fabricated MoS2 nanoflowers-modified graphite felt (GF-MoS2) to construct the electrochemical apparatus (EA) and adsorption column (AC), attempting to stable and effective Cr(VI) removal at neutral pHs via electrochemical Cr(VI) reduction and subsequent Cr(III) adsorption. In EA with a sequential oxidation-reduction process, Cr(VI)-contaminated influent (5 mg/L) at neutral pHs (6.0-8.0) was oxidized first by anode to generate large amounts of H+ ions via H2O oxidation, decreasing the pH of anode-oxidized influent to ∼2.5 at 2.6 V and 1000 L/m2/h. Subsequently, the acidic anode-oxidized influent was further reduced by GF-MoS2 cathode, promoting significantly Cr(VI) reduction via decreasing Cr(VI) oxidation potentials and alleviating Cr(III) precipitation on cathode. These results enabled the stable and effective operation of GF-MoS2-based EA with almost Cr(VI) reduction to Cr(III). With further assembling GF-MoS2-based AC, Cr(III) species in EA effluent were easily adsorbed or intercepted by GF-MoS2, achieving undetectable Cr species in AC effluent. Combination techniques of GF-MoS2-based electrochemical reduction and adsorption can be an effective approach for remediating Cr(VI)-contaminated water at neutral pHs.

Enhanced removal of phenanthrene and nutrients in wetland sediment with metallic biochar: Performance and mechanisms.

Polycyclic aromatic hydrocarbon (PAHs) are persistent organic pollutants and pose high risk in aquatic environment. The utilization of biochar is a strategy for PAHs-contaminated remediation but is challenging due to the adsorption saturation and reoccurrence of PAHs desorbed back into water. In this study, iron (Fe) and manganese (Mn) were provided as electron acceptors for biochar modification to enhance anaerobic biodegradation of phenanthrene (Phe). Results revealed that, the Mn(Ⅳ) and Fe(Ⅲ) modification improved the removal of Phe by 24.2% and 31.4% than that of biochar, respectively. Additionally, nitrate removal was improved by 19.5% with Fe(Ⅲ) amendment. The Mn-and Fe-biochar decreased Phe contents by 8.7% and 17.4% in sediment, 10.3% and 13.8% in biochar than that of biochar. Much higher DOC contents were observed with Mn- and Fe-biochar, which provided bioavailable carbon source for microbes and contributed to microbial degradation of Phe. The greater degree of humification, higher proportions of humic and fulvic acid like components in metallic biochar participated in electron transport and further enhancing the degradation of PAHs. Microbial analysis proved the high abundance of Phe-degrading bacteria (e.g. PAH-RHDα, Flavobacterium and Vibrio), nitrogen removal microbes (e.g. amoA, nxrA, and nir), Fe and Mn bioreduction or oxidation (e. g. Bacillus, Thermomonas, Deferribacter) with metallic biochar. Based on the results, the Fe and Mn modification, especially Fe-modified biochar provided well performance for PAHs removal in aquatic sediment.

A stable superatomic Cu6(SMPP)6 nanocluster with dual emission.

We have synthesized single crystals of a highly stable Cu6 nanocluster protected by six ligands of 2-mercapto-5-n-propylpyrimidine (SMPP). This Cu6(SMPP)6 cluster has a quasi-octahedral superatomic Cu6 core, with the Cu atoms being protected by both -S- and N-bidentate coordination of the SMPP ligands. Interestingly, each Cu atom is linked with an N atom, while the two neighboring Cu atoms on the same triangular facet are linked by the -S- bridge of the ligand. Single-crystal parsing results show that the altered orientation of the SMPP ligands give rise to three packing modes (named as 1, 2, and 3) of the Cu6(SMPP)6 NCs. Apart from the well-organized coordination, this Cu6(SMPP)6 nanocluster exhibits superatomic stability with a metallic core of 4 valence electrons (1S22S2||3S2), enabling to largely balance the interactions between the polynuclear core and delocalized electrons. Interestingly, the Cu6(SMPP)6 NCs display dual emissions in both ultraviolet-visible (UV-Vis) and near-infrared (NIR) regions. First-principles calculations well reproduce the experimental spectrum, shedding light on the nature of excitation states and metal-ligand interactions in the Cu6(SMPP)6 cluster.

Enhancement of organics and nutrient removal and microbial mechanism in vertical flow constructed wetland under a static magnetic field.

Low and unstable pollutant removal is regarded as the bottleneck problem in constructed wetlands (CWs) for wastewater treatment. This study investigated the effect of static magnetic field (MF) on enhancing the purification efficiency and microbial mechanism in vertical flow CW systems for treating domestic wastewater. The results showed that MF-CWs outperformed control systems in terms of treatment performance, with average removal efficiencies of COD, NH4+-N, TN, and TP reaching 92.58%, 73.58%, 72.53%, and 95.83%, respectively. The change of malondialdehyde (MDA), catalase (CAT), and superoxide dismutase (SOD) activity indicated that MF application was beneficial for plant health. Additionally, higher ammonia monooxygenase (AMO) activity in MF-CWs suggested the removal of NH4+-N was facilitated. The high-throughput sequencing results demonstrated that MF application could enrich the functional bacteria such as Patescibacteria phylum, mainly, including Gammaproteobacteria, Betaproteobacteria, and Alphaproteobacteria, which further accelerated pollutants transformation. These findings would be beneficial in understanding pollutant removal processes and their mechanism in CWs with MF application.

Effects of multiple key factors on the performance of petroleum coke-based constructed wetland-microbial fuel cell.

In this study, two constructed wetland-microbial fuel cells (CW-MFC), including a closed-circuit system (CCW-MFC) and an open-circuit system (OCW-MFC) with petroleum coke as electrode and substrate, were constructed to explore the effect of multiple key factors on their operation performances. Compared to a traditional CW, the CCW-MFC system showed better performance, achieving an average removal efficiency of COD, NH4+-N, and TN of 94.49 ± 1.81%, 94.99 ± 4.81%, and 84.67 ± 5.6%, respectively, when the aeration rate, COD concentration, and hydraulic retention time were 0.4 L/min, 300 mg/L, and 3 days. The maximum output voltage (425.2 mV) of the CCW-MFC system was achieved when the aeration rate was 0.2 L/min. In addition, the CCW-MFC system showed a greater denitrification ability due to the higher abundance of Thiothrix that might attract other denitrifying bacteria, such as Methylotenera and Hyphomicrobium, to participate in the denitrifying process, indicating the quorum sensing could be stimulated within the denitrifying microbial community.