Unveiling the fate of metal leaching in bimetal-catalyzed Fenton-like systems: pivotal role of aqueous matrices and machine learning prediction.

Metal-based catalytic materials exhibit exceptional properties in degrading emerging pollutants within Fenton-like systems. However, the potential risk of metal leaching has become pressing environmental concern. This study addressed scientific issues pertaining to the leaching behavior and control strategies for metal-based catalytic materials. Innovative cobalt-aluminum hydrotalcite (CoAl-LDH) triggered peroxymonosulfate (PMS) activation system was constructed and achieved near-complete removal of Ciprofloxacin (CIP) across diverse water quality environments. Notably, it was found that the tunable ion exchange and Al3+ stabilization of CoAl-LDH occurred due to the particularity of neutral water quality, resulting in significantly lower Co2+ leaching levels (0.321 mg/L) compared to acidic conditions (5.103 mg/L). In light of this, machine learning technology was then employed for the first time to simulate the dynamic trend of Co2+ leaching and elucidated the critical regulatory roles and mechanisms of Al3+, aqueous matrix, and reaction rate. Furthermore, degradation systems based on different water quality and metal leaching levels regulated the generation levels of SO4.- and O2∙-, and the unique advantages of free radical attack paths were clarified through CIP degradation products and ecotoxicity analysis. These findings introduced novel insights and approaches for engineering application and pollution control in metal-based Fenton-like water treatment.

Sequential bio-treatment of ammonia-rich wastewater from Chinese medicine residue utilization: Regulation of dissolved oxygen.

To effectively treat actual ammonia-rich Chinese medicine residue (CMR) resource utilization wastewater, we optimized an anaerobic-microaerobic two-stage expanded granular sludge bed (EGSB) and moving bed sequencing batch reactor (MBSBR) combined process. By controlling dissolved oxygen (DO) levels, impressive removal efficiencies were achieved. Microaeration, contrasting with anaerobic conditions, bolstered dehydrogenase activity, enhanced electron transfer, and enriched the functional microorganism community. The increased relative abundance of Synergistetes and Proteobacteria facilitated hydrolytic acidification and fostered nitrogen and phosphorus removal. Furthermore, we examined the impact of DO concentration in MBSBR on pollutant removal and microbial metabolic activity, pinpointing 2.5 mg/L as the optimal DO concentration for superior removal performance and energy conservation.

Feedback of chain elongation microorganisms on iron-based conductive materials: Enhanced microbial functions and biotoxicity adaptation mechanisms.

Despite the increased research efforts aimed at understanding iron-based conductive materials (CMs) for facilitating chain elongation (CE) to produce medium chain fatty acids (MCFAs), the impact of these materials on microbial community functions and the adaptation mechanisms to their biotoxicity remain unclear. This study found that the supply of zero-valent iron (ZVI) and magnetite enhanced the MCFAs carbon-flow distribution by 26 % and 52 %, respectively. Metagenomic analysis revealed the upregulation of fatty acid metabolism, pyruvate metabolism and ABC transporters with ZVI and magnetite. The predominant functional microorganisms were Massilibacterium and Tidjanibacter with ZVI, and were Petrimonas and Candidatus_Microthrix with magnetite. Furthermore, it was demonstrated that CE microorganisms respond and adapt to the biotoxicity of iron-based CMs by adjusting Two-component system and Quorum sensing for the first time. In summary, this study provided a new deep-insight on the feedback mechanisms of CE microorganisms on iron-based CMs.

Upgrading soybean dreg to caproate via intermediate of lactate and mediator of biochar.

To address the environmental hazards posed by high-yield soybean dreg (SD), a high-value strategy is firstly proposed by synthesizing caproate through chain elongation (CE). Optimized conditions for lactate-rich broth as intermediate, utilizing 50 % inoculum ratio, 40 g/L substrate concentration, and pH 5, resulting in 2.05 g/L caproate from direct fermentation. Leveraging lactate-rich broth supplemented with ethanol, caproate was optimized to 2.76 g/L under a refined electron donor to acceptor of 2:1. Furthermore, incorporating 20 g/L biochar elevated caproate production to 3.05 g/L and significantly shortened the lag phase. Mechanistic insights revealed that biochar's surface-existed quinone and hydroquinone groups exhibit potent redox characteristics, thereby facilitating electron transfer. Moreover, biochar up-regulated the abundance of key genes involved in CE process (especially fatty acids biosynthesis pathway), also enriching Lysinibacillus and Pseudomonas as an unrecognized cooperation to CE. This study paves a way for sustainable development of SD by upgrading to caproate.

How denitrifiers defense ciprofloxacin: Insights from intracellular and extracellular stress response.

Overuse of antibiotics has led to their existence in nitrogen-containing water. The impacts of antibiotics on bio-denitrification and the metabolic response of denitrifiers to antibiotics are unclear. We systematically analyzed the effect of ciprofloxacin (CIP) on bio-denitrification and found that 5 mg/L CIP greatly inhibited denitrification with a model denitrifier (Paracoccus denitrificans). Nitrate reduction decreased by 32.89 % and nitrous oxide emission increased by 75.53 %. The balance analysis of carbon and nitrogen metabolism during denitrification showed that CIP exposure blocked electron transfer and reduced the flow of substrate metabolism used for denitrification. Proteomics results showed that CIP exposure induced denitrifiers to use the pentose phosphate pathway more for substrate metabolism. This caused a substrate preference to generate NADPH to prevent cellular damage rather than NADH for denitrification. Notably, despite denitrifiers having antioxidant defenses, they could not completely prevent oxidative damage caused by CIP exposure. The effect of CIP exposure on denitrifiers after removal of extracellular polymeric substances (EPS) demonstrated that EPS around denitrifiers formed a barrier against CIP. Fluorescence and infrared spectroscopy revealed that the binding effect of proteins in EPS to CIP prevented damage. This study shows that denitrifiers resist antibiotic stress through different intracellular and extracellular defense strategies.

Enhancing simultaneous nitrogen and phosphorus availability through biochar addition during Chinese medicinal herbal residues composting: Synergism of microbes and humus.

The disposal of Chinese medicinal herbal residues (CMHRs) derived from Chinese medicine extraction poses a significant environmental challenge. Aerobic composting presents a sustainable treatment method, yet optimizing nutrient conversion remains a critical concern. This study investigated the effect and mechanism of biochar addition on nitrogen and phosphorus transformation to enhance the efficacy and quality of compost products. The findings reveal that incorporating biochar considerably enhanced the process of nutrient conversion. Specifically, biochar addition promoted the retention of bioavailable organic nitrogen and reduced nitrogen loss by 28.1 %. Meanwhile, adding biochar inhibited the conversion of available phosphorus to non-available phosphorus while enhancing its conversion to moderately available phosphorus, thereby preserving phosphorus availability post-composting. Furthermore, the inclusion of biochar altered microbial community structure and fostered organic matter retention and humus formation, ultimately affecting the modification of nitrogen and phosphorus forms. Structural equation modeling revealed that microbial community had a more pronounced impact on bioavailable organic nitrogen, while humic acid exerted a more significant effect on phosphorus availability. This research provides a viable approach and foundation for regulating the levels of nitrogen and phosphorus nutrients during composting, serving as a valuable reference for the development of sustainable utilization technologies pertaining to CMHRs.

How hetero-single-atom dispersion reconstructed electronic structure of carbon materials and regulated Fenton-like oxidation pathways.

Single-atom catalysts (SACs) have emerged as competitive candidates for Fenton-like oxidation of micro-pollutants in water. However, the impact of metal insertion on the intrinsic catalytic activity of carrier materials has been commonly overlooked, and the environmental risk due to metal leaching still requires attention. In contrast to previous reports, where metal sites were conventionally considered as catalytic centers, our study investigates, for the first time, the crucial catalytic role of the carbon carrier modulated through hetero-single-atom dispersion and the regulation of Fenton-like oxidation pathways. The inherent differences in electronic properties between Fe and Co can effectively trigger long-range electron rearrangement in the sp2-carbon-conjugated structure, creating more electron-rich regions for peroxymonosulfate (PMS) complexation and initiating the electron transfer process (ETP) for pollutant degradation, which imparts the synthesized catalyst (FeCo-NCB) with exceptional catalytic efficiency despite its relatively low metal content. Moreover, the FeCo-NCB/PMS system exhibits enduring decontamination efficiency in complex water matrices, satisfactory catalytic stability, and low metal leaching, signifying promising practical applications. More impressively, the spatial relationship between metal sites and electron density clouds is revealed to determine whether high-valent metal-oxo species (HVMO) are involved during the decomposition of surface complexes. Unlike single-type single-atom dispersion, where metal sites are situated within electron-rich regions, hetero-single-atom dispersion can cause the deviation of electron density clouds from the metal sites, thus hindering the in-situ oxidation of metal within the complexes and minimizing the contribution of HVMO. These findings provide new insights into the development of carbon-based SACs and advance the understanding of nonradical mechanisms underpinning Fenton-like treatments.

Enhanced Oxidation of Organic Compounds by the Ferrihydrite-Ferrate System: The Role of Intramolecular Electron Transfer and Intermediate Iron Species.

Previous studies mostly held that the oxidation capacity of ferrate depends on the involvement of intermediate iron species (i.e., FeIV/FeV), however, the potential role of the metastable complex was disregarded in ferrate-based heterogeneous catalytic oxidation processes. Herein, we reported a complexation-mediated electron transfer mechanism in the ferrihydrite-ferrate system toward sulfamethoxazole (SMX) degradation. A synergy between intermediate FeIV/FeV oxidation and the intramolecular electron transfer step was proposed. Specifically, the conversion of phenyl methyl sulfoxide (PMSO) to methyl phenyl sulfone (PMSO2) suggested that FeIV/FeV was involved in the oxidation of SMX. Moreover, based on the in situ Raman test and chronopotentiometry analysis, the formation of the metastable complex of ferrihydrite/ferrate was found, which possesses higher oxidation potential than free ferrate and could achieve the preliminary oxidation of organics via the electron transfer step. In addition, the amino group of SMX could complex with ferrate, and the resulting metastable complex of ferrihydrite/ferrate would combine further with SMX molecules, leading to intramolecular electron transfer and SMX degradation. The ferrate loss experiments suggested that ferrihydrite could accelerate the decomposition of ferrate. Finally, the effects of pH value, anions, humic acid, and actual water on the degradation of SMX by ferrihydrite-ferrate were also revealed. Overall, ferrihydrite demonstrated high catalytic capacity, good reusability, and nontoxic performance for ferrate activation. The ferrihydrite-ferrate process may be a green and promising method for organic removal in wastewater treatment.

Attenuation effects of ZVI/PDS pretreatment on propagation of antibiotic resistance genes in bioreactors: Driven by antibiotic residues and sulfate assimilation.

Sulfate radical-based advanced oxidation processes (AOPs) combined biological system was a promising technology for treating antibiotic wastewater. However, how pretreatment influence antibiotic resistance genes (ARGs) propagation remains largely elusive, especially the produced by-products (antibiotic residues and sulfate) are often ignored. Herein, we investigated the effects of zero valent iron/persulfate pretreatment on ARGs in bioreactors treating sulfadiazine wastewater. Results showed absolute and relative abundance of ARGs reduced by 59.8%- 81.9% and 9.1%- 52.9% after pretreatments. The effect of 90-min pretreatment was better than that of the 30-min. The ARGs reduction was due to decreased antibiotic residues and stimulated sulfate assimilation. Reduced antibiotic residues was a major factor in ARGs attenuation, which could suppress oxidative stress, inhibit mobile genetic elements emergence and resistant strains proliferation. The presence of sulfate in influent supplemented microbial sulfur sources and facilitated the in-situ synthesis of antioxidant cysteine through sulfate assimilation, which drove ARGs attenuation by alleviating oxidative stress. This is the first detailed analysis about the regulatory mechanism of how sulfate radical-based AOPs mediate in ARGs attenuation, which is expected to provide theoretical basis for solving concerns about by-products and developing practical methods to hinder ARGs propagation.

Enhanced in-situ sludge reduction of the side-stream process via employing micro-aerobic approach in both mainstream and side-stream.

Side-stream reactor (SSR), as an in-situ sludge reduction process with high sludge reduction efficiency (SRE) and less negative impact on effluent, has been widely researched. In order to reduce cost and promote large-scale application, the anaerobic/anoxic/micro-aerobic/oxic bioreactor coupled with micro-aerobic SSR (AAMOM) was used to investigate nutrient removal and SRE under short hydraulic retention time (HRT) of SSR. When HRT of SSR was 4 h, AAMOM system achieved 30.41% SRE, while maintaining carbon and nitrogen removal efficiency. Micro-aerobic in mainstream accelerated the hydrolysis of particulate organic matter (POM) and promoted denitrification. Micro-aerobic in side-stream increased cell lysis and ATP dissipation, thus increasing SRE. Microbial community structure indicated that the cooperative interactions among hydrolytic, slow growing, predatory and fermentation bacteria played key roles in improving SRE. This study confirmed that SSR coupled micro-aerobic was a promising and practical process, which could benefit nitrogen removal and sludge reduction in municipal wastewater treatment plants.

Machine learning approaches to predict the apparent rate constants for aqueous organic compounds by ferrate.

The apparent second-order rate constant with hexavalent ferrate (Fe(VI)) (kFe(VI)) is a key indicator to evaluate the removal efficiency of a molecule by Fe(VI) oxidation. kFe(VI) is often determined by experiment, but such measurements can hardly catch up with the rapid growth of organic compounds (OCs). To address this issue, in this study, a total of 437 experimental second-order kFe(VI) rate constants at a range of conditions (pH and temperature) were used to train four machine learning (ML) algorithms (lasso regression (LR), ridge regression (RR), extreme gradient boosting (XGBoost), and the light gradient boosting machine (LightGBM)). Using the Morgan fingerprint (MF)) of a range of organic compounds (OCs) as the input, the performance of the four algorithms was comprehensively compared with respect to the coefficient of determination (R2) and root-mean-square error (RMSE). It is shown that the RR, XGBoost, and LightGBM models displayed generally acceptable performance kFe(VI) (R2test > 0.7). In addition, the shapely additive explanation (SHAP) and feature importance methods were employed to interpret the XGBoost/LightGBM and RR models, respectively. The results showed that the XGBoost/LightGBM and RR models suggestd pH as the most important predictor and the tree-based models elucidate how electron-donating and electron-withdrawing groups influence the reactivity of the Fe(VI) species. In addition, the RR model share eight common features, including pH, with the two tree-based models. This work provides a fast and acceptable method for predicting kFe(VI) values and can help researchers better understand the degradation behavior of OCs by Fe(VI) oxidation from the perspective of molecular structure.

Electro-peroxone pretreatment for enhanced simulated hospital wastewater treatment and antibiotic resistance genes reduction.

Hospital wastewater is one of the possible sources responsible for antibiotic resistant bacteria spread into the environment. This study proposed a promising strategy, electro-peroxone (E-peroxone) pretreatment followed by a sequencing batch reactor (SBR) for simulated hospital wastewater treatment, aiming to enhance the wastewater treatment performance and to reduce antibiotic resistance genes production simultaneously. The highest chemical oxygen demand (COD) and total organic carbon (TOC) removal efficiency of 94.3% and 92.8% were obtained using the E-peroxone-SBR process. The microbial community analysis through high-throughput sequencing showed that E-peroxone pretreatment could guarantee microbial richness and diversity in SBR, as well as reduce the microbial inhibitions caused by antibiotic and raise the amount of nitrification and denitrification genera. Specially, quantitative real-time PCRs revealed that E-peroxone pretreatment could largely reduce the numbers and contents of antibiotic resistance genes (ARGs) production in the following biological treatment unit. It was indicated that E-peroxone-SBR process may provide an effective way for hospital wastewater treatment and possible ARGs reduction.

Continuous energy recovery and nutrients removal from molasses wastewater by synergistic system of dark fermentation and algal culture under various fermentation types.

Synergistic system of dark fermentation and algal culture was initially operated at batch mode to investigate the energy production and nutrients removal from molasses wastewater in butyrate-type, ethanol-type and propionate-type fermentations. Butyrate-type fermentation was the most appropriate fermentation type for the synergistic system and exhibited the accumulative hydrogen volume of 658.3 mL L-1 and hydrogen yield of 131.7 mL g-1 COD. By-products from dark fermentation (mainly acetate and butyrate) were further used to cultivate oleaginous microalgae. The maximum algal biomass and lipid content reached 1.01 g L-1 and 38.5%, respectively. In continuous operation, the synergistic system was stable and efficient, and energy production increased from 8.77 kJ L-1 d-1 (dark fermentation) to 17.3 kJ L-1 d-1 (synergistic system). Total COD, TN and TP removal efficiencies in the synergistic system reached 91.1%, 89.1% and 85.7%, respectively. This study shows the potential of the synergistic system in energy recovery and wastewater treatment.

Effect of metabolic uncoupler, 3,3',4',5-tetrachlorosalicylanilide (TCS) on Bacillus subtilis: biofilm formation, flocculability and surface characteristics.

In order to understand the inhibitory mechanism of metabolic uncoupler in biofilm, this study investigated the effect of TCS on B. subtilis biofilm formation, flocculability, surface characteristics and thermodynamic properties. An optimal concentration of TCS, a metabolic uncoupler, was observed to substantially inhibit biofilm formation and the secretion of extracellular polymeric substances (EPS). The effect of TCS on the zeta potential and flocculability of bacterial suspension implied the addition of 100 µg L-1 TCS increased the net negative charge of cell surface which induced the reduction of B. subtilis flocculability. Meanwhile, the effects of TCS on bacterial surfacial thermodynamic properties were analyzed by the Derjaguin-Landau-Verwey-Overbeek (DLVO) and extend DLVO (XDLVO) theories. As DLVO and XDLVO predicted, the primary energy barrier between bacterial cells incubated with 100 µg L-1 TCS were increased compared to that of control, indicating that B. subtilis incubated with 100 µg L-1 TCS must consume more energy to aggregate or form biofilm.

Continuous hydrogen production from glucose/xylose by an anaerobic sequential batch reactor to maximize the energy recovery efficiency.

Fermentation of both glucose and xylose is essential to realize efficient bioconversion of renewable and abundant lignocellulosic biomass to hydrogen. In this study, a mixture of glucose and xylose at different ratios was used as a substrate for biological hydrogen production by an anaerobic sequential batch reactor (ASBR). An average glucose and xylose consumption of 80% and 50% with a high hydrogen production rate of 7.1 ± 0.9 mmol L-1 h-1 was obtained, respectively. Hydraulic retention time (HRT) played a critical role in hydrogen production at high glucose to xylose ratios. A maximum hydrogen production rate of 8.9 mmol L-1 h-1 was achieved at an optimized HRT of 12 h with a high glucose and xylose consumption of 92.2% and 82.2%, respectively. Upon further energy conversion analysis, continuous hydrogen production by ASBR provided the maximum energy conversion efficiency of 21.5%. These results indicate that ASBR can effectively accelerate the hydrogen production rate, improve substrate consumption regardless of the glucose to xylose ratio, and thus provides a new direction for efficient hydrogen production from lignocellulosic feedstock.

Enhancing sludge biodegradability and volatile fatty acid production by tetrakis hydroxymethyl phosphonium sulfate pretreatment.

A new pretreatment method based on tetrakis hydroxymethyl phosphonium sulfate (THPS) biocide was tried to enhance sludge disintegration, and improved sludge biodegradability and subsequent volatile fatty acid (VFA) production. Sludge activity decreased to less than 10% after 2 days pretreatment using 20mg/g-TSS THPS, which also obviously destroyed EPS and cell membrane, and dissolved more biodegradable substances (48.8%) than raw sludge (19.7%). Moreover, 20mg/g-TSS THPS pretreatment shortened fermentation time to 4days and improved VFA production to 2778mg COD/L (4.35 times than that in control). Therein, the sum of n-butyric, n-valeric and iso-valeric acids unexpectedly accounted for 60.5% of total VFA (only 20.1% of that in control). The more high molecular weight VFAs (C4-C5) than low molecular VFAs (C2-C3) resulted from THPS pretreatment benefited to subsequent medium-chain volatile acids (C6-C12) generation to realize the separation and recovery of organic carbon more efficiently.

Nutrients and COD removal of swine wastewater with an isolated microalgal strain Neochloris aquatica CL-M1 accumulating high carbohydrate content used for biobutanol production.

In this study, a carbohydrate-rich microalga Neochloris aquatica CL-M1 was adapted to grow in swine wastewater. The effects of cultivation conditions (i.e., temperature, light intensity or N/P ratio) on COD/nutrients removal and carbohydrate-rich biomass production were investigated. The results indicate that the highest COD removal (81.7%) and NH3-N removal (96.2%) was achieved at 150µmolm-2s-1 light intensity, 25°C and N/P ratio=1.5/1. The highest biomass concentration and carbohydrate content was 6.10gL-1 and 50.46%, respectively, when N/P ratio=5/1. The resulting carbohydrate-rich microalgal biomass was pretreated and used as a feedstock for butanol fermentation. With the initial sugar concentration of 48.7gL-1 glucose and 3.4gL-1 xylose in the pretreated biomass, the butanol concentration, yield, and productivity were 12.0gL-1, 0.60molmol-1 sugar, and 0.89gL-1h-1, respectively, indicating the high potential of using Neochloris aquatica CL-M1 for butanol fermentation.

Biological phosphorus removal in an extended ASM2 model: Roles of extracellular polymeric substances and kinetic modeling.

This paper presents the results of an extended ASM2 model for the modeling and calibration of the role of extracellular polymeric substances (EPS) in phosphorus (P) removal in an anaerobic-aerobic process. In this extended ASM2 model, two new components, the bound EPS (XEPS) and the soluble EPS (SEPS), are introduced. Compared with the ASM2, 7.71, 8.53, and 9.28% decreases in polyphosphate (polyP) were observed in the extended ASM2 in three sequencing batch reactors feeding with different COD/P ratios, indicating that 7.71-9.28% of P in the liquid was adsorbed by EPS. Sensitive analysis indicated that, five parameters were the significant influential parameters and had been chosen for further model calibration by using the least square method to simulate by MATLAB. This extended ASM2 has been successfully established to simulate the output variables and provides a useful reference for the mathematic simulations of the role of EPS in biological phosphorus removal process.

Mathematical modeling of simultaneous carbon-nitrogen-sulfur removal from industrial wastewater.

A mathematical model of carbon, nitrogen and sulfur removal (C-N-S) from industrial wastewater was constructed considering the interactions of sulfate-reducing bacteria (SRB), sulfide-oxidizing bacteria (SOB), nitrate-reducing bacteria (NRB), facultative bacteria (FB), and methane producing archaea (MPA). For the kinetic network, the bioconversion of C-N by heterotrophic denitrifiers (NO3-→NO2-→N2), and that of C-S by SRB (SO42-→S2-) and SOB (S2-→S0) was proposed and calibrated based on batch experimental data. The model closely predicted the profiles of nitrate, nitrite, sulfate, sulfide, lactate, acetate, methane and oxygen under both anaerobic and micro-aerobic conditions. The best-fit kinetic parameters had small 95% confidence regions with mean values approximately at the center. The model was further validated using independent data sets generated under different operating conditions. This work was the first successful mathematical modeling of simultaneous C-N-S removal from industrial wastewater and more importantly, the proposed model was proven feasible to simulate other relevant processes, such as sulfate-reducing, sulfide-oxidizing process (SR-SO) and denitrifying sulfide removal (DSR) process. The model developed is expected to enhance our ability to predict the treatment of carbon-nitrogen-sulfur contaminated industrial wastewater.

Enhanced volatile fatty acid production from excess sludge by combined free nitrous acid and rhamnolipid treatment.

VFA production from excess sludge (ES) was greatly enhanced by a low-cost and high-efficient treatment: 0.67mg/L free nitrous acid (FNA) pretreatment combined with 0.04g/g TSS rhamnolipid (RL) addition (FNA+RL), which significantly shortened fermentation time to 3days and increased VFA production to 352.26mgCOD/g VSS (5.42 times higher than raw ES). Propionic and acetic acids were the two leading components (71.86% of the total VFA). Mechanism investigation manifested FNA+RL improved the biodegradability of ES, achieved positive synergetic effect on solubilization, hydrolysis and acidification efficiencies, and inhibited methanation. Microbial community distribution further explained the above phenomena. The bacteria related to polysaccharides/protein utilization and VFA generation, including Clostridium, Megasphaera and Proteiniborus, were mainly observed in FNA+RL, whereas gas-forming bacteria Anaerolineae and acid-consuming bacteria Proteobacteria were assuredly suppressed. Besides, Propionibacterineae associated with propionic acid generation was exclusively enriched in sole RL and FNA+RL.