Mechanism Involved in Polyvinyl Chloride Nanoplastics Induced Anaerobic Granular Sludge Disintegration: Microbial Interaction Energy, EPS Molecular Structure, and Metabolism Functions.

Nanoplastics (NPs) are emerging pollutants and have been reported to cause the disintegration of anaerobic granular sludge (AnGS). However, the mechanism involved in AnGS disintegration was not clear. In this study, polyvinyl chloride nanoplastics (PVC-NPs) were chosen as target NPs and their long-term impact on AnGS structure was investigated. Results showed that increasing PVC-NPs concentration resulted in the inhibition of acetoclastic methanogens, syntrophic propionate, and butyrate degradation, as well as AnGS disintegration. At the presence of 50 µg·L-1 PVC-NPs, the hydrophobic interaction was weakened with a higher energy barrier due to the relatively higher hydrophilic functional groups in extracellular polymeric substances (EPS). PVC-NPs-induced ROS inhibited quorum sensing, significantly downregulated hydrophobic amino acid synthesis, whereas it highly upregulated the genes related to the synthesis of four hydrophilic amino acids (Cys, Glu, Gly, and Lys), resulting in a higher hydrophily degree of protein secondary structure in EPS. The differential expression of genes involved in EPS biosynthesis and the resulting protein secondary structure contributed to the greater hydrophilic interaction, reducing microbial aggregation ability. The findings provided new insight into the long-term impact of PVC-NPs on AnGS when treating wastewater containing NPs and filled the knowledge gap on the mechanism involved in AnGS disintegration by PVC-NPs.

1D Covalent Organic Frameworks Triggering Highly Efficient Photosynthesis of H2 O2 via Controllable Modular Design.

The topological diversity of covalent organic frameworks (COFs) enables considerable space for exploring their structure-performance relationships. In this study, we report a sequence of novel 1D COFs (EO, ES, and ESe-COF) with typical 4-c sql topology that can be interconnected with VIA group elements (O, S, and Se) via a modular design strategy. It is found that the electronic structures, charge delivery property, light harvesting ability, and hydrophilicity of these 1D COFs can be profoundly influenced by the bridge-linked atom ordinal. Finally, EO-COF, possessing the highest quantity of active sites, the longest lifetime of the active electron, the strongest interaction with O2 , and the lowest energy barrier of O2 reduction, exhibits exceptional photocatalytic O2 -to-H2 O2 activity under visible light, with a production rate of 2675 µmol g-1 h-1 and a high apparent quantum yield of 6.57 % at 450 nm. This is the first systematic report on 1D COFs for H2 O2 photosynthesis, which enriches the topological database in reticular chemistry and promotes the exploration of structure-catalysis correlation.

The humic substance analogue antraquinone-2, 6-disulfonate (AQDS) enhanced zero-valent iron based autotrophic denitrification: Performances and mechanisms.

Zero-valent iron based autotrophic denitrification (ZVI-AD) has attracted increasing attentions in nitrate removal due to saving organic carbon budget in wastewater treatment, but limited by the low reaction speed, poor electron transfer efficiency as well as the compaction/blocking by iron hydrolysis products. Humic substances (HS) were promising to regulate iron cycle and accelerate electron transfer by serving as electron mediators. In this study, HS analogue, antraquinone-2, 6-disulfonate (AQDS), was added to enhance ZVI-AD process. Results showed that the dosage of AQDS led to a NO3--N removal efficiency of 83.37 ± 3.98% within 96 h, which was 32.28 ± 1.25% higher than that in ZVI-AD system. The corrosion of ZVI and microbially nitrate reduction were both improved at the presence of AQDS. The addition of AQDS enriched the functional species, including autotrophic denitrobacteria namely Thauera and Hydrogenophaga, iron redox-related species namely Ferruginibacter and HS respiration related species namely Flavobacterium. The genes napA and napB related to electron transfer, nirK and nosZ related to the accumulation of intermediate products were also enriched by the addition of AQDS. AQDS addition boosted the electrons flowing to both abiotic and biotic nitrate reduction. Nitrate removal mechanism involved in ZVI-AQDS coupled system was proposed. This study provided an alternative strategy for improving ZVI-AD by HS.

Biomass-Induced Diphasic Carbon Decoration for Carbon Nitride: Band and Electronic Engineering Targeting Efficient N2 Photofixation.

Boosting the replacement of traditional NH3 production (Haber-Bosch process) with photocatalytic technology is of great importance for energy and environment remediation. Herein, to develop a photocatalyst with efficient charge separation and abundant reactive sites for photocatalytic N2 fixation, a biomass-induced diphase-carbon doping strategy is proposed by adding lotus root starch which can be environmentally produced into the preparation of carbon nitride (CN). The adjustment to the CN framework by planar-fused carbon optimizes the band alignment of the catalyst, improving its response to sunlight. In particular, the in-plane-fused carbon in collaboration with the physically piled carbon initiates unique dual electron transfer pathways from different dimensions. The diphasic carbons can both function as qualified reactive sites according to the experimental explorations and further theoretical calculations, which effectively regulate the electron transfer and energy barrier associated with the N2 reduction on catalyst. The bio-carbon-doped catalyst exhibits drastically enhanced photocatalytic N2 fixation performance, and the NH3 yield on the optimized DC-CN0.1 reaches 167.35 µmol g-1 h-1 , which is fivefold of g-C3 N4 and stands far out from the single-phase doped systems. These explorations expand the metal-free skeleton engineering toolbox and provide new guidance for the solar energy utilizations.

Efficient removal of Sb(â ¤) from water using sulphidated ferrihydrite via tripuhyite (FeSbO4) precipitation and complexation.

Elevated concentrations of antimony (Sb) in the ecological environment have received considerable attention due to the harmful consequence involved. This study synthesized sulphidated ferrihydrite with different S:Fe molar ratios to efficiently remove Sb(V) from water. As the S:Fe molar ratio ranged from 0.00 to 1.48, the removal efficiency of Sb(V) by sulphidated ferrihydrite first decreased before increasing considerably. Sulphidated ferrihydrite with an S:Fe molar ratio of 0.74 exhibited a strong affinity towards Sb(V) with an optimal removal capacity of 963.74 mg Sb/g, which was 3.2-fold higher than that of ferrihydrite. In the kinetic experiments, the removal behavior of Sb(V) was well described by the pseudo-second-order model, suggesting that the removal process was controlled via chemisorption. Moreover, Sb(V) was efficiently removed over a wide pH range of 3.00-11.00, and coexisting anions (NO3-, Cl-, SO42-, SiO32-, CO32- and PO43-) exhibited marginal impact on the Sb(V) removal by sulphidated ferrihydrite (S:Fe ≥ 0.44). The characterization results of XRD, SEM, TEM mapping and etched XPS revealed goethite to be the dominant phase of sulphidated ferrihydrite with an S:Fe molar ratio of 0.15, while a mixed constitution of mixed-valent iron (hydro)oxides and iron sulphide was formed when the S:Fe molar ratio exceeded 0.44. Moreover, sulphidated ferrihydrite acted as a donor for Fe and S for the effective retention of Sb(V) by two main pathways: precipitation (tripuhyite, FeSbO4) and complexation (≡S-H and ≡Fe-OH). Therefore, sulphidated ferrihydrite is a promising material for eliminating Sb(V) contamination from water.

Coupled biodegradation of p-nitrophenol and p-aminophenol in bioelectrochemical system: Mechanism and microbial functional diversity.

Biodegradation mechanisms and microbial functional diversity during coupled p-nitrophenol (PNP) and p-aminophenol (PAP) degradation were studied in a bioelectrochemical system. PNP in the biocathode and PAP in the bioanode were almost completely removed within 28hr and 68hr respectively. The degradation followed the steps including hydrating hydroxyalkylation, dehydrogenating carbonylation, and hydrolating ring cleavage, etc. Metagemomic analysis based on the KEGG and eggNOG database annotations revealed the microbial composition and functional genes/enzymes related to phenol degradation in the system. The predominant bacteria genera were Lautropia, Pandoraea, Thiobacillus, Ignavibacterium, Truepera and Hyphomicrobium. The recognized biodegradation genes/enzymes related to pollutant degradation were as follows: pmo, hbd, & ppo for phenol degradation, nzba, amie, & badh for aromatic degradation, and CYP & p450 for xenobiotics degradation, etc. The co-occurrence of ARGs (antibiotic resistant genes), such as adeF, MexJ, ErmF, PDC-93 and Escherichia_coli_mdfA, etc., were annotated in CARD database during the biodegradation process. The Proteobacteria & Actinobacteria phylum was the primary host of both the biodegradation genes & ARGs in this system. The microbial functional diversity ensured the effective biodegradation of the phenol pollutants in the bioelectrochemical system.

Functional Group-Dependent Screening of Organophosphate Esters (OPEs) and Discovery of an Abundant OPE Bis-(2-ethylhexyl)-phenyl Phosphate in Indoor Dust.

There is increasing scientific interest in environmental pollution and the effect on public health caused by organophosphate esters (OPEs). Using liquid chromatography coupled to a hybrid quadrupole Orbitrap high-resolution mass spectrometer, a novel, robust, and untargeted screening strategy for the identification of novel OPEs in indoor dust samples was presently developed based on the characteristic molecular fragmentation pathways, and 12 previously reported OPEs and six previously unrecognized OPEs were detected in the combined extracts of indoor dust samples, collected in Nanjing, eastern China. One of the six detected OPEs, bis-(2-ethylhexyl)-phenyl phosphate (BEHPP), was identified by comparison of unique LC and MS characteristics with a synthesized pure standard. Accurate concentrations of BEHPP were determined in n = 50 individual indoor dust samples with 100% detection frequency with a median concentration range of 50-1530 ng/g dry weight, which were generally greater or at least comparable to traditional OPEs, that is, triphenyl phosphate and 2-ethylhexyl diphenyl phosphate (EHDPP), in the same dust samples. Statistically significant, positive correlations were found for log-transformed concentrations of BEHPP versus EHDPP (r2 = 0.7884, p < 0.0001), and BEHPP versus tris(2-ethylhexyl)phosphate (r2 = 0.4054, p < 0.0001), suggesting their similar commercial applications and sources in the environment.

A novel acetogenic bacteria isolated from waste activated sludge and its potential application for enhancing anaerobic digestion performance.

The development of anaerobic digestion (AD) for volatile fatty acids (VFAs) production from waste activated sludge (WAS) is arrested due to low hydrolysis and acidification efficiency. This study proposed to enhance WAS reduction and VFAs accumulation during AD process via bioaugmentation of acetate-producing bacteria. Four acetogens were firstly isolated from a temperature-phased anaerobic digestion (TPAD) system. The acetate production efficiency of different isolates ranged from 15.8 to 73.7 mg acetate/g TOC, in which the bacterial strain NJUST19 was found to be the most effective strain. The results of morphological, biochemical characteristics as well as phylogenetic analysis showed that the isolate NJUST19 was Gram-positive and rod-shaped, catalase-negative, nitrate reduction-positive, methyl red-negative and capable of starch and gelatin hydrolysis, for which the name of Clostridium sp. NJUST19 was proposed. The optimal culture conditions (i.e. initial pH and temperature) were evaluated for their effects on microbe growth of selected NJUST19, and the maximum acetate production was observed at pH 9.0 and temperature of 40 °C. In the case of modified TPAD system inoculated with Clostridium sp. NJUST19, total suspended solids (TSS) removal rate and maximum VFAs accumulation increasing to 35.3% and 4200 mg/L, respectively, which was much higher than that of control (21.9% and 2894 mg/L). These results indicated that Clostridium sp. NJUST 19 is capable of enhancing digestion efficiency with a great benefit for VFAs production, offering potential prospects for bioaugmentation of WAS anaerobic digestion.

Organophosphate Ester, 2-Ethylhexyl Diphenyl Phosphate (EHDPP), Elicits Cytotoxic and Transcriptomic Effects in Chicken Embryonic Hepatocytes and Its Biotransformation Profile Compared to Humans.

The effects of 2-ethylhexyl diphenyl phosphate (EHDPP) on cytotoxicity and mRNA expression, as well as its metabolism, were investigated using a chicken embryonic hepatocyte (CEH) assay. After incubation for 36 h, the lethal concentration 50 (LC50) was 50 ± 11 µM, suggesting that EHDPP is one of a small cohort of highly toxic organophosphate esters (OPEs). By use of a ToxChip polymerase chain reaction (PCR) array, we report modulation of 6, 11, or 16/43 genes in CEH following exposure to 0.1, 1, or 10 µM EHDPP, respectively. The altered genes were from all nine biological pathways represented on the ToxChip including bile acids/cholesterol regulation, glucose metabolism, lipid homeostasis, and the thyroid hormone pathway. After incubation for 36 h, 92.5% of EHDPP was transformed, and one of its presumed metabolites, diphenyl phosphate (DPHP), only accounted for 12% of the original EHDPP concentration. Further screening by use of high-resolution mass spectrometry revealed a novel EHDPP metabolite, hydroxylated 2-ethylhexyl monophenyl phosphate (OH-EHMPP), which was also detected in a human blood pool. Additional EHDPP metabolites detected in the human blood pool included EHMPP and DPHP. Overall, this study provided novel information regarding the toxicity of EHDPP and identified a potential EHDPP metabolite, OH-EHMPP, in both avian species and humans.

Simultaneous pyridine biodegradation and nitrogen removal in an aerobic granular system.

Simultaneous pyridine biodegradation and nitrogen removal were successfully achieved in a sequencing batch reactor (SBR) based on aerobic granules. In a typical SBR cycle, nitritation occurred obviously after the majority of pyridine was removed, while denitrification occurred at early stage of the cycle when oxygen consumption was aggravated. The effect of several key operation parameters, i.e., air flow rate, influent NH4+-N concentration, influent pH and pyridine concentration, on nitritation, pyridine degradation and total nitrogen (TN) removal, was systematically investigated. The results indicated that high air flow rate had a positive effect on both pyridine degradation and nitritation but a negative impact of overhigh air flow rate. With the increase of NH4+ dosage, both nitritation and TN removal could be severely inhibited. Slightly alkaline condition, i.e., pH7.0-8.0, was beneficial for both pyridine degradation and nitritation. High pyridine dosage often resulted in the delay of both pyridine degradation and nitritation. Besides, extracellular polymeric substances production was affected by air flow rate, NH4+ dosage, pyridine dosage and pH. In addition, high-throughput sequencing analysis demonstrated that Bdellovibrio and Paracoccus were the dominant species in the aerobic granulation system. Coexistence of pyridine degrader, nitrification related species, denitrification related species, polymeric substances producer and self-aggregation related species was also confirmed by high-throughput sequencing.

Electrospun flexible poly(bisphenol A carbonate) nanofibers decorated with Ag nanoparticles as effective 3D SERS substrates for trace TNT detection.

A flexible 3D hybrid PC/Ag surface-enhanced Raman scattering (SERS) substrate was fabricated through the combination of electrospinning and in situ chemical reduction. Due to the rough surface morphology and the intricate 3D structure, a high density of Raman "hotspots" was formed at the junctions of cross-linked nanofibers, resulting in excellent sensitivity to a probe molecule (4-aminothiophenol). The nanofibers were modified with l-cysteine to capture TNT molecules by the formation of a Meisenheimer complex, after which positively charged 4-ATP-labelled AgNPs were introduced to the system, which both generated more hotspots and led to a linear relationship between the TNT concentration and the SERS intensity of the labelled molecules. As a result, a good linear response ranging from 10-8 to 10-12 M was achieved, and the detection limit for TNT was as low as 2.05 × 10-13 M. This strategy demonstrates an ultra-sensitive approach for the detection of trace amounts of TNT, and a promising method for the detection of many other analogous explosives.

Reuse of Fenton sludge as an iron source for NiFe2O4 synthesis and its application in the Fenton-based process.

The potentially hazardous iron-containing sludge from the Fenton process requires proper treatment and disposal, which often results in high treatment cost. In this study, a novel method for the reuse of Fenton sludge as an iron source for the synthesis of nickel ferrite particles (NiFe2O4) is proposed. Through a co-precipitation method followed by sintering at 800°C, magnetic NiFe2O4 particles were successfully synthesized, which was confirmed by powder X-ray diffraction (XRD), scanning electronic microscopy (SEM), energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FT-IR) and Raman spectroscopy. The synthesized NiFe2O4 could be used as an efficient catalyst in the heterogeneous Fenton process. In phenol degradation with H2O2 or NiFe2O4 alone, the phenol removal efficiencies within the reaction time of 330min were as low as 5.9%±0.1% and 13.5%±0.4%, respectively. However, in the presence of both NiFe2O4 and H2O2, phenol removal efficiency as high as 95%±3.4% could be achieved, indicating the excellent catalytic performance of NiFe2O4 in the heterogeneous Fenton process. Notably, a rapid electron exchange between NiII and FeIII ions in the NiFe2O4 structure could be beneficial for the Fenton reaction. In addition, the magnetic catalyst was relatively stable, highly active and recoverable, and has potential applications in the Fenton process for organic pollutant removal.

Removal of multi-substituted nitroaromatic pollutants by zero valent iron: a comparison of performance, kinetics, toxicity and mechanisms.

Reductive degradation of three typical multi-substituted nitroaromatic pollutants by zero valent iron was comprehensively compared in terms of performance, kinetics, toxicity and mechanisms in this study. The results showed that 0.5 mM 2,4-dinitrochlorobenzene (DNCB), 2,4-dinitroanisole (DNAN) and 2,4-dinitrophenol (DNP) could be completely removed in the ZVI reduction system within 75 min, 90 min and 210 min, respectively. The pseudo first-order kinetics could well describe the reduction process of the three NACs by ZVI. The reduction rates of the three NACs follow the order of DNCB > DNAN > DNP, which was further confirmed by density functional theory computational analysis. Moreover, the acute toxicity of the three NAC effluents significantly decreased after treatment with ZVI. In addition, the mechanistic investigation revealed that the selective reduction of nitro groups on the three NACs was closely related to the characteristics of the functional groups on the benzene rings. The results of this study would increase the comprehensive understanding in terms of their performance, kinetics, toxicity and mechanisms involved in the reduction of multi-substituted NACs by ZVI, thus benefiting the effective treatment of wastewaters containing multi-substituted nitroaromatic pollutants due to ZVI.

Stable operation of microbial fuel cells at low temperatures (5­10 °C) with light exposure and its anodic microbial analysis.

Performances of microbial fuel cells (MFCs) were studied at 5­10 and 25­30 °C. Results showed stable operation of the MFCs at low temperatures with only slight reductions of voltage and power generation (11 versus 14 % for double-chamber MFC, while 14 versus 21 % for single-chamber MFC, 1,000 Ω) compared to those at mesophilic temperatures. MFCs operated at low temperatures showed lower COD removal rates accompanied by higher coulombic efficiencies (CEs). PCR-DGGE analysis revealed that psychrotrophic microbes (mainly Arcobacter, Pseudomonas, and Geobacter) dominated on anodes of the MFCs at low temperatures. Interestingly, light-induced red substances appeared on anode of the MFCs operated at low temperature and were proven to be the main anodic microbes (Arcobacter and Pseudomonas). Co-existence of the aforementioned microbes could assist stable low-temperature operation of the MFCs. Cyclic voltammetry analysis supported the results of the CE and DGGE. Stable performance of MFCs at low temperatures might be achieved by the control of anodic bacteria.

Kinetics study of pyridine biodegradation by a novel bacterial strain, Rhizobium sp. NJUST18.

Biodegradation of pyridine by a novel bacterial strain, Rhizobium sp. NJUST18, was studied in batch experiments over a wide concentration range (from 100 to 1,000 mg l(-1)). Pyridine inhibited both growth of Rhizobium sp. NJUST18 and biodegradation of pyridine. The Haldane model could be fitted to the growth kinetics data well with the kinetic constants µ* = 0.1473 h(-1), K s = 793.97 mg l(-1), K i = 268.60 mg l(-1) and S m = 461.80 mg l(-1). The true µ max, calculated from µ*, was found to be 0.0332 h(-1). Yield coefficient Y X/S depended on S i and reached a maximum of 0.51 g g(-1) at S i of 600 mg l(-1). V max was calculated by fitting the pyridine consumption data with the Gompertz model. V max increased with initial pyridine concentration up to 14.809 mg l(-1) h(-1). The q S values, calculated from [Formula: see text], were fitted with the Haldane equation, yielding q Smax = 0.1212 g g(-1) h(-1) and q* = 0.3874 g g(-1) h(-1) at S m' = 507.83 mg l(-1), K s' = 558.03 mg l(-1), and K i' = 462.15 mg l(-1). Inhibition constants for growth and degradation rate value were in the same range. Compared with other pyridine degraders, µ max and S m obtained for Rhizobium sp. NJUST18 were relatively high. High K i and K i' values and extremely high K s and K s' values indicated that NJUST18 was able to grow on pyridine within a wide concentration range, especially at relatively high concentrations.

Removal of phosphate from wastewater using alkaline residue.

Alkaline residue (AR) was found to be an efficient adsorbent for phosphate removal from wastewater. The kinetic and equilibrium of phosphate removal were investigated to evaluate the performance of modified alkaline residue. After treatment by NaOH (AR-NaOH), removal performance was significantly improved, while removal performance was almost completely lost after treatment by HCl (AR-HCl). The kinetics of the removal process by all adsorbents was well characterized by the pseudo second-order model. The Langmuir model exhibited the best correlation for AR-HCl, while AR was effectively described by Freundlich model. Both models were well fitted to AR-NaOH. The maximum adsorption capacities calculated from Langmuir equation were in following manner: AR-NaOH > AR > AR-HCl. Phosphate removal by alkaline residue was pH dependent process. Mechanisms for phosphate removal mainly involved adsorption and precipitation, varied with equilibrium pH of solution. For AR-HCl, the acid equilibrium pH (< 6.0) was unfavorable for the formation of Ca-P precipitate, with adsorption as the key mechanism for phosphate removal. In contrast, for AR and AR-NaOH, precipitation was the dominant mechanism for phosphate removal, due to the incrase on pH (> 8.0) after phosphate removal. The results of both XRD and SEM analysis confirmed CaHPO4·2H2O formation after phosphate removal by AR and AR-NaOH.

Glycine betaine modulates extracellular polymeric substances to enhance microbial salinity tolerance.

High salinity inhibits microbial activity in the bioremediation of saline wastewater. To alleviate osmotic stress, glycine betaine (GB), an osmoprotectant, is added to enhance the secretion of extracellular polymeric substances (EPS). These EPS are pivotal in withstanding environmental stressors, yet the intricate interplay between GB supplementation and microbial responses through EPS modifications-encompassing composition, molecular architecture, and electrochemical features-remains elusive in hypersaline conditions. Here we show microbial strategies for salinity endurance by investigating the impact of GB on the dynamic alterations of EPS properties. Our findings reveal that GB supplementation at 3.5% salinity elevates the total EPS (T-EPS) content from 12.50 ± 0.05 to 24.58 ± 0.96 mg per g dry cell weight. The observed shift in zeta potential from -28.95 to -6.25 mV at 0% and 3.5% salinity, respectively, with GB treatment, indicates a reduction in electrostatic repulsion and compaction. Notably, the EPS protein secondary structure transition from ß-sheet to α-helix, with GB addition, signifies a more compact protein configuration, less susceptible to salinity fluctuations. Electrochemical analyses, including cyclic voltammetry (CV) and differential pulse voltammetry (DPV), reveal GB's role in promoting the release of exogenous electron shuttles, such as flavins and c-type cytochromes (c-Cyts). The enhancement in DPV peak areas (QDPV) with GB addition implies an increase in available extracellular electron transfer sites. This investigation advances our comprehension of microbial adaptation mechanisms to salinity through EPS modifications facilitated by GB in saline habitats.

Effects of nitrate reduction on the biotransformation of 1H-1,2,4-triazole: Mechanism and community evolution.

Due to the refractory of 1 H-1,2,4-triazole (TZ), conventional anaerobic biological treatment technology is usually restricted by low removal efficiency and poor system stability. In this study, TZ biodegradation and nitrate reduction was coupled to improve the removal efficiency of TZ from polluted wastewater. Batch assay was performed with pure culture strain Raoultella sp. NJUST42, which was reported to have the capability to degrade TZ in our previous study. Based on batch assay result, complete removal of TZ could be achieved in the presence of nitrate, whereas only 50% of TZ could be removed in the control system. Long-term stability experiment indicated that the relative abundance of microorganisms (Bacteroidetes_vadinHA17, Georgenia, Anaerolinea, etc) was obviously enhanced under nitrate reduction condition. During long-term period, major intermediates for TZ biodegradation such as [1,2,4]Triazolidine-3,5-diol, hydrazine dibasic carboxylic acid and carbamic acid were detected. A novel TZ biotransformation approach via hydration, TZ-ring cleavage, deamination and oxidation was speculated. PICRUSt1 and KEGG pathway analyses indicated that hydration (dch), oxidation (adhD, oah, pucG, fdhA) of TZ and nitrate reduction (Nar, napA, nrfA, nirBK, norB, nosZ) were significantly enhanced in the presence of nitrate. Moreover, the significant enrichment of TCA cycle (gab, sdh, fum, etc.) indicated that carbon and energy metabolism were facilitated with the addition of nitrate, thus improved TZ catabolism. The proposed mechanism demonstrated that TZ biodegradation coupled with nitrate reduction would be a promising approach for efficient treatment of wastewater contaminated by TZ.

Ammonia monooxygenase-mediated cometabolic biotransformation of volatile 4-chlorophenol in nitrifying counter-diffused biofilms: A combined molecular dynamics simulation, DFT calculation and experimental study.

Ammonia monooxygenase (AMO)-mediated cometabolism of organic pollutants has been widely observed in biological nitrogen removal process. However, its molecular mechanism remains unclear, hindering its practical application. Furthermore, conventional nitrification systems encounter significant challenges such as air pollution and the loss of ammonia-oxidizing bacteria, when dealing with wastewater containing volatile organic pollutants. This study developed a nitrifying membrane-aerated biofilm reactor (MABR) to enhance the biodegradation of volatile 4-chlorophenol (4-CP). Results showed that 4-CP was primarily removed via Nitrosomonas nitrosa-mediated cometabolism in the presence of NH4+-N, supported by the increased nicotinamide adenine dinucleotide (NADH) and adenosine triphosphate (ATP) content, AMO activity and the related genes abundance. Hydroquinone, detected for the first time and produced via oxidative dechlorination, as well as 4-chlorocatechol was primary transformation products of 4-CP. Nitrosomonas nitrosa AMO structural model was constructed for the first time using homology modeling. Molecular dynamics simulation suggested that the ortho-carbon in the benzene ring of 4-CP was more prone to metabolismcompared to the ipso-carbon. Density functional theory calculation revealed that 4-CP was metabolized by AMO via H-abstraction-OH-rebound reaction, with a significantly higher rebound barrier at the ipso-carbon (16.37 kcal·mol-1) as compared to the ortho-carbon (6.7 kcal·mol-1). This study fills the knowledge gap on the molecular mechanism of AMO-mediated cometabolism of organic pollutants, providing practical and theoretical foundations for improving volatile organic pollutants removal through nitrifying MABR.

New insights into algal-bacterial sludge granulation based on the tightly-bound extracellular polymeric substances regulation in response to N-Methylpyrrolidone.

Algal-bacterial granular sludge (ABGS) system is promising in wastewater treatment for its potential in energy-neutrality and carbon-neutrality. However, traditional cultivation of ABGS poses significant challenges attributable to its long start-up period and high energy consumption. Extracellular polymeric substances (EPS), which could be stimulated as a self-defense strategy in cells under toxic contaminants stress, has been considered to contribute to the ABGS granulation process. In this study, photogranulation of ABGS by EPS regulation in response to varying loading rates of N-Methylpyrrolidone (NMP) was investigated for the first time. The results indicated the formation of ABGS with a maximum average diameter of ∼3.3 mm and an exceptionally low SVI5 value of 67 ± 2 mL g-1 under an NMP loading rate of 125 mg L-1 d-1, thereby demonstrating outstanding settleability. Besides, almost complete removal of 300 mg L-1 NMP could be achieved at hydraulic retention time of 48 h, accompanied by chemical oxygen demand (COD) and total nitrogen (TN) removal efficiencies higher than 90 % and 70 %, respectively. Moreover, possible degradation pathway and metabolism mechanism in the ABGS system for enhanced removal of NMP and nitrogen were proposed. In this ABGS system, the mycelium with network structure constituted by filamentous microorganisms was a prerequisite for photogranulation, instead of necessarily leading to granulation. Stress of 100-150 mg L-1 d-1 NMP loading rate stimulated tightly-bound EPS (TB-EPS) variation, resulting in rapid photogranulation. The crucial role of TB-EPS was revealed with the involved mechanisms being clarified. This study provides a novel insight into ABGS development based on the TB-EPS regulation by NMP, which is significant for achieving the manipulation of photogranules.