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Impact of freeze-thaw cycles and influent C/N ratios on N2O emissions in subsurface wastewater infiltration systems

Subsurface wastewater infiltration system (SWIS) is important source of N2O emission, biological denitrification process relies on organic carbon source as electron donor, enabling denitrifying reductase (NAR, NIR, NOR, and N2OR) to reduce nitrate nitrogen to N2. However, freeze-thaw cycles cause changes in soil structure through physical and biological processes that increase organic matter availability and microbial activity, thereby accelerating upper (aerobic) organic matter degradation. This leads to carbon deficiency in the lower (anaerobic) layer, which reduces denitrification efficiency increasing N2O production and emissions. This study investigated effects of influent C/N ratios on N2O emissions from SWIS under freeze-thaw stress, and changes in denitrifying reductase and microbial communities. Results showed that as influent C/N ratio increased from 6:1–10:1, average TN removal of SWIS decreased from 89.59 % to 84.95 %, while N2O emission rate decreased from 0.106 mg·m−2·h−1 to 0.0333 mg·m−2·h−1, a reduction of 68.61 %. Meanwhile, N2OR activity increased by 29.95 % with C/N ratio increasing from 6 to 10, showing a significant reduction of N2O. High-throughput sequencing results revealed that Proteobacteria and Firmicutes showed a linear relationship with influent C/N. As C/N increased from 6 to 8 and 10, Proteobacteria relative abundance increased from 22.24 % ± 1.79–32.51 % ± 2.51 % and 39.59 % ± 3.45 %, while Firmicutes relative abundance decreased from 31.73 % ± 7.87–3.34 % ± 0.27 % and 2.19 % ± 0.07 %. These results indicated that sufficient supply of organic carbon provided abundant electron donors for denitrifying reductases in freeze-thaw-affected SWIS, promoting influent NO3--N reduction and decreasing N2O release rates. Conversely, under low C/N ratio conditions, electron acceptance capacity of N2OR was limited and N2OR activity was inhibited, resulting in N2O accumulation and emission. SynopsisThis paper shows how increasing the organic carbon supply in SWIS can reduce N2O emissions and improve nitrogen removal under freeze-thaw stress.

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Experimental investigation of CO2 capture at high pressure using energy-efficient amino acid salt solvents

The increase in energy consumption has led to greenhouse gas emissions, specifically CO2. This has caused many researchers to explore the possibility of capturing CO2 emissions. The utilization of typical water-based solvents, such as amine solutions, poses challenges in large-scale operations owing to the substantial energy consumption associated with their regeneration process. To decrease the energy required to regenerate the solvent, new types of phase change solvents, known as lean water amino acid-based phase change solvents, were invented. This study investigated the absorption capacity of an amino acid salt made up of glutamine and potassium hydroxide in a water-based solution including N,N-dimethylformamide (DMF) as a co-solvent. The measurement of absorption capacity was conducted under elevated pressures ranging from 5 to 30 bar. Additionally, an investigation was conducted to assess the impact of DMF volumetric concentration on absorption capacity. The findings of the study indicated that augmenting both the pressure and concentration of DMF increased the capacity for CO2 absorption. This enhancement was achieved by simultaneously raising the rates of physical and chemical absorption. The results obtained from the C NMR phase analysis revealed that the solid phase had carbon bonds that were related to the absorption of CO2, whilst the upper liquid phase did not contain any CO2. This phase might readily be recycled into the absorption process without the need for regeneration. The absorption capacity of this solvent was also assessed following three absorption-reduction cycles. The results indicated a decrease in absorption capacity by only 6.6 %.

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Decoupling study of municipal solid waste gasification: Effect of pelletization on pyrolysis and gasification of pyrolytic char

To explore the influence of pelletization on the thermal conversion of municipal solid waste (MSW), pyrolysis characteristics and gasification reactivity of MSW pellet and powder were investigated in this study. Besides, the physicochemical properties of internal char and external char within the char pellet were separately characterized. Moreover, the relationship between the physicochemical properties of char pellet and its gasification reactivity was clarified. Results showed that the pyrolytic gas yields of MSW pellets were increased by 15.47 % and 11.55 % at 700 °C and 800 °C, respectively, compared to powder MSW. It was mainly attributed that the conversion of monocyclic aromatic hydrocarbons to polycyclic aromatic hydrocarbons was promoted by the longer residence time within the pellets. Meanwhile, the physicochemical properties of pyrolytic char pellets exhibited a significant heterogeneity. Specifically, the number of ordered aromatic rings of char pellet was reduced, while the order degree of carbon structure was enhanced, particularly the internal char. However, the difference magnitude between internal and external char was diminished with temperature. This was due to the higher temperature resulting in a larger surface specific area and pore volume of the char pellet, especially the internal char, thereby enhancing the pyrolysis process. Furthermore, an increase in pore volume within the char pellet improved gasification reactivity when the conversion rate > 0.4. These findings provide a reference for the pyrolysis and gasification process of MSW pellets.

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Z-scheme H-PDI supermolecule/NH2-MIL-101(Fe) for enhanced malathion degradation: Mechanism, pathway, and toxicity assessment

Malathion (MA) is a widely used organophosphorus pesticide globally. Developing efficient photocatalysts is crucial for eliminating MA pollution in water by photocatalytic technology. This study focuses on preparing a series of H-PDI supermolecule/NH2-MIL-101(Fe) (PM) materials by amidating NH2-MIL-101(Fe) with the more stable H-PDI supermolecule, forming a covalent OC–NH bond. Among these materials, 40 %PM (indicating a mass percentage content of 40 % H-PDI supermolecule in PM) exhibited the best performance for degradation of MA. Under simulated sunlight irradiation of a 10 mg·L1 MA solution for 180 min, the reaction rate constants of 40 %PM were 5.95 times and 3.13 times higher than those of NH2-MIL-101(Fe) and H-PDI supermolecule, respectively. The enhanced performance is attributed to the formation of Z-scheme heterojunctions in the 40 %PM composite lead to fast separation of photogenerated e− and h+. Combining the results of HPLC-MS with Fukui Function, the HOMO, LUMO, and pathway of degradation of MA attracted by 1O2, •OH, and h+ were speculated. The pathway involves oxidation, demethylation, P-S bond breakage, decarboxylation, and final conversion to some inorganic molecules. The toxicity of the degradation byproducts were lower than that of MA estimated by Toxicity Estimation Software Tool.

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Rapid bromate determination using short-column ion chromatography-mass spectrometry: Application to bromate quantification during ozonation

A streamlined, precise, and dependable method for the concurrent quantification of bromate has been established, employing ion chromatography in conjunction with electrospray ionization tandem mass spectrometry (IC-ESI-MS/MS). In an effort to expedite sample analysis duration, the AG18 short column was utilized for rapid separation of the specified analytes. Utilizing a blend of water and acetonitrile as the mobile phase within an optimized gradient elution setting, it was possible to achieve satisfactory resolution in under 3 minutes. Specifically, the mixing of acetonitrile in water samples improves the sensitivity and immunity of the method. This phenomenon may be attributed to the similar proportions of acetonitrile in the sample and the mobile phase, which effectively reduces the viscosity and surface tension of the droplets during the ESI process. Detection limits and quantification thresholds were 0.14 µg/L and 0.41 µg/L, respectively. Analyte recoveries, when spiked into tap water between 2.5 µg/L to 50 µg/L, ranged from 69.5 % to 116.7 %; precision metrics, measured as intra- and inter-day relative standard deviations, spanned 5.1–7.9 %. The devised approach encountered minimal interference from prevalent water matrix constituents, including chloride (50–200 mg/L), sulfate (25–200 mg/L), bicarbonate/carbonate (1–6 mM), and natural organic matter (1–8 mg/L). In environmental contexts, this methodology effectively tracked the production of bromate in controlled ozonation experiments conducted in the laboratory. Segmented ozone dosing reduced bromate production when the solution contained low concentrations of DOC, which provides an alternative strategy for controlling bromate production.

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Electrochemically activated persulfate combined with tannic acid significantly improved sludge-dewatering performance: Sludge floc weight structure, Fe(II)/Fe(III), and organic component conversion

Sludge-dewatering effect is a key factor in sludge disposal. In this study, the conditioning system of electrochemically activated persulfate combined with tannic acid (EF-PDS/TA) was used to improve sludge-dewatering performance. Results showed that the sludge water content (Wc) and Specific resistance to filtration (SRF) decreased by 29.4 % and 93.3 %, respectively, under the optimal operating conditions, which significantly improved the sludge-dewatering effect. Through research, we found that SO4•− and ·OH were the main factors promoting the improvement in sludge-dewatering performance. After the reaction, the physicochemical properties of the sludge changed significantly, and the floc structure effectively cracked. Further analysis of Fe2+/Fe3+ conversion, EEM and FTIR showed that in the process of sludge conditioning, on the basis of EF promoting Fe2+/Fe3+ conversion through electron transfer between cathode and anode plates, TA addition further improved the conversion efficiency of Fe2+/Fe3+. The conversion rate was as high as 90 %, which improved the oxidation ability of sludge. The thermal energy generated by the EF ohmic heat effect can promote the complexation and precipitation of proteins in EPS by TA, and the energy can be effectively utilized. Moreover, EF and TA exerted a synergistic effect in promoting Fe2+/Fe3+ conversion and protein cleavage. Finally, the economic cost of the combined conditioning system was calculated, and the practical application value of the conditioning system was evaluated. The findings laid a theoretical foundation for further research in the field of advanced sludge oxidation.

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Catalytic activity insight into sustainable Fe-hydroxyapatite application using an experimental design approach

Combining experimental design with advanced characterisation methods provides a valuable opportunity to deepen our understanding of catalytic processes and their underlying mechanisms. Here, a series of hydroxyapatite doped with Fe2+ at different molar loadings noted HAP-FeX% (X = 1; 5.5 and 10; Ca/Fe molar ratio) were elaborated using a one-pot synthesis method. Characterization of these catalysts by various techniques such as ICP, BET/BJH, TGA/DSC, XRD, Raman, UV–visible, TPD-NH3, SEM, and TEM revealed substantial Fe2+ oxidation during synthesis, inducing changes in the morphological and physical-chemical characteristics of HAP caused by Fe3+/Ca2+ substitution. Furthermore, the synthesis produced nanoparticles (approximately 0.30 nm in size) on the hydroxyapatite surface, resulting from the precipitation of Fe/O phases. The catalysts exhibited good catalytic performance in methylene blue (MB) degradation through the photo-Fenton process (95 %). The Ca/Fe molar ratio = 8.8 %, [H2O2] = 2.8 mmol L−1, and pH = 8.8 were optimized using the design of experiments (DOE) via response surface methodology (RSM). A mathematical model was developed to determine the influence of the Ca2+/Fe3+ substitution and the Fe/O phase on the catalytic activity. The results revealed the role of the Fe/O phase in the reaction initiation and the surface modification induced by Ca2+/Fe3+ substitution to facilitate the reaction chain.

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