Co-utilization of wastewater sludge and heavy metals for single-atom electrocatalytic reduction of gaseous CO2.

Synergetic management of waste activated sludge, heavy metals (HMs) and CO2 for their valorization and cyclic utilization is rarely reported. Herein, we employed sludge-derived extracellular polymeric substances (EPS) and HMs in wastewater to fabricate a gas diffusion electrode (GDE) for electrochemical CO2 reduction. This approach atomically dispersed Ni at each nanofiber of the GDE. Abundant N element in the EPS proved to play a key role in the formation of Nx-Ni (mixture of N3-Ni and N4-Ni) sites for highly efficient CO2 to CO conversion. The atomical Ni3+ shows high catalytic activity. Direct gaseous CO2 reduction in a membrane electrode assembly generated a current density up to 50 mA·cm-2 with CO:H2 ratio of ∼100 and ∼75% FECO under 2.69 cell voltage. This strategy takes advantage of all waste streams generated on site and consolidates traditionally separated treatment processes to save costs, produces value-added products and generates carbon benefits during wastewater treatment.

The insightful water quality analysis and predictive model establishment via machine learning in dual-source drinking water distribution system.

Dual-source drinking water distribution systems (DWDS) over single-source water supply systems are becoming more practical in providing water for megacities. However, the more complex water supply problems are also generated, especially at the hydraulic junction. Herein, we have sampled for a one-year and analyzed the water quality at the hydraulic junction of a dual-source DWDS. The results show that visible changes in drinking water quality, including turbidity, pH, UV254, DOC, residual chlorine, and trihalomethanes (TMHs), are observed at the sample point between 10 and 12 km to one drinking water plant. The average concentration of residual chlorine decreases from 0.74 ± 0.05 mg/L to 0.31 ± 0.11 mg/L during the water supplied from 0 to 10 km and then increases to 0.75 ± 0.05 mg/L at the end of 22 km. Whereas the THMs shows an opposite trend, the concentration reaches to a peak level at hydraulic junction area (10-12 km). According to parallel factor (PARAFAC) and high-performance size-exclusion chromatography (HPSEC) analysis, organic matters vary significantly during water distribution, and tryptophan-like substances and amino acids are closely related to the level of THMs. The hydraulic junction area is confirmed to be located at 10-12 km based on the water quality variation. Furthermore, data-driven models are established by machine learning (ML) with test R2 higher than 0.8 for THMs prediction. And the SHAP analysis explains the model results and identifies the positive (water temperature and water supply distance) and negative (residual chlorine and pH) key factors influencing the THMs formation. This study conducts a deep understanding of water quality at the hydraulic junction areas and establishes predictive models for THMs formation in dual-sources DWDS.

Artificial Soil-Like Material Enhances CO2 Bio-Valorization into Chemicals in Gas Fermentation.

Gas fermentation offers a carbon-neutral route for producing industrial feedstocks using autotrophic microbes to convert carbon dioxide (CO2) in waste gases, such as industrial emissions and biogas, into valuable chemicals or biofuels. However, slow microbial metabolism owing to low gaseous solubility causes significant challenges in gas fermentation. Although chemical or genetic manipulations have been explored to improve gas fermentation, they are either nonsustainable or complex. Herein, an artificial soil-like material (SLM) inspired by natural soil was fabricated to improve the growth and metabolism ofCupriavidus necatorfor enhanced poly-ß-hydroxybutyrate (PHB) biosynthesis from CO2 and hydrogen (H2). Porous SLM comprises low-cost nanoclay, boehmite, and starch and serves as a biocarrier to facilitate the colonization of bacteria and delivery of CO2 to bacteria. With 3.0 g/L SLM addition, the solubility of CO2 in water increased by ∼4 times and biomass and PHB production boosted by 29 and 102%, respectively, in the 24 h culture. In addition, a positive modulation was observed in the metabolism of PHB biosynthesis. PHB biosynthesis-associated gene expression was found to be enhanced in response to the SLM addition. The concentrations of intermediates in the metabolic pathway of PHB biosynthesis, such as pyruvate and acetyl-CoA, as well as reducing energy (ATP and NADPH) significantly increased with SLM addition. SLM also demonstrated the merits of easy fabrication, high stability, recyclability, and plasticity, thereby indicating its considerable potential for large-scale application in gas fermentation.

How Nitrogen and Sulfur Doping Modified Material Structure, Transformed Oxidation Pathways, and Improved Degradation Performance in Peroxymonosulfate Activation.

Current research has widely applied heteroatom doping for the promotion of catalyst activity in peroxymonosulfate (PMS) systems; however, the relationship between heteroatom doping and stimulated activation mechanism transformation is not fully understood. Herein, we introduce nitrogen and sulfur doping into a Co@rGO material for PMS activation to degrade tetracycline (TC) and systematically investigate how heteroatom doping transformed the activation mechanism of the original Co@rGO/PMS system. N was homogeneously inserted into the reduced graphene oxide (rGO) matrix of Co@rGO, inducing a significant increase in the degradation efficiency without affecting the activation mechanism transformation. Additionally, S doping converted Co3O4 to Co4S3 in Co@rGO and transformed the cooperative oxidation pathway into a single non-radical pathway with stronger intensity, which led to a higher stability against environmental interferences. Notably, based on density functional theory (DFT) calculations, we demonstrated that Co4S3 had a higher energy barrier for PMS adsorption and cleavage than Co3O4, and therefore, the radical pathway was not easily stimulated by Co4S3. Overall, this study not only illustrated the improvement due to the heteroatom doping of Co@rGO for TC degradation in a PMS system but also bridged the knowledge gap between the catalyst structure and degradation performance through activation mechanism transformation drawn from theoretical and experimental analyses.

Why the cooperation of radical and non-radical pathways in PMS system leads to a higher efficiency than a single pathway in tetracycline degradation.

Current research focused on developing multiple active species in peroxymonosulfate (PMS) system to degrade contaminants, but deepening concern lacks over why cooperation of those active species facilitated a faster degradation. Here, we employed Co3O4, rGO and Co3O4@rGO composite to activate PMS for tetracycline (TC) degradation, and detected crucial factors toward highest performance of Co3O4@rGO/PMS system. Batch experiments exhibited a satisfactory TC degradation efficiency under Co3O4@rGO/PMS, complete degraded 50 mg/L TC within 20 min. Analytical tests discovered that radical active species generated by Co3O4/PMS and non-radical species by rGO/PMS were successfully co-existed in Co3O4@rGO/PMS system, significantly improving the performance of TC removal. Subsequently, a combination of density functional theory (DFT) calculation and intermediates analysis revealed that, in Co3O4@rGO/PMS system, the cooperation rather than independent effect of radical and non-radical active species expanded TC degradation pathways, enhancing the degradation performance. Furthermore, decent adaptability, stability, and recyclability toward affecting factors variation of Co3O4@rGO/PMS demonstrated it as a potent and economical system to degrade TC. Overall, this study developed a novel Co3O4@rGO/PMS system with a cooperative oxidation pathway for highly efficient TC removal, and managed to clarify why this oxidation pathway achieved high efficiency through a combination of theoretical and experimental method.

Pilot Study on the Combination of Different Pre-Treatments with Nanofiltration for Efficiently Restraining Membrane Fouling While Providing High-Quality Drinking Water.

Nanofiltration (NF) is a promising post-treatment technology for providing high-quality drinking water. However, membrane fouling remains a challenge to long-term NF in providing high-quality drinking water. Herein, we found that coupling pre-treatments (sand filtration (SF) and ozone-biological activated carbon (O3-BAC)) and NF is a potent tactic against membrane fouling while achieving high-quality drinking water. The pilot results showed that using SF+O3-BAC pre-treated water as the feed water resulted in a lower but a slowly rising transmembrane pressure (TMP) in NF post-treatment, whereas an opposite observation was found when using SF pre-treated water as the feed water. High-performance size-exclusion chromatography (HPSEC) and three-dimensional excitation-emission matrix (3D-EEM) fluorescence spectroscopy determined that the O3-BAC process changed the characteristic of dissolved organic matter (DOM), probably by removing the DOM of lower apparent molecular weight (LMW) and decreasing the biodegradability of water. Moreover, amino acids and tyrosine-like substances which were significantly related to medium and small molecule organics were found as the key foulants to membrane fouling. In addition, the accumulation of powdered activated carbon in O3-BAC pre-treated water on the membrane surface could be the key reason protecting the NF membrane from fouling.

Transfer characteristic of fluorine from atmospheric dry deposition, fertilizers, pesticides, and phosphogypsum into soil.

Fluorine (F) is widely dispersed in the environment and frequently used in industry and agriculture with a high migration ability. Thus, it is essential to understand the leaching characteristic of F in soil from industry and agriculture sources. Several sources of F pollutants in soil, including fertilizers, pesticides, phosphogypsum, and atmospheric deposition, were selected to investigate leaching characteristics of F in soil by leaching experiments. The addition of phosphate fertilizer and compound fertilizer (N:P:K = 20:10:15) enhanced the leachability of F in soil and the proportion of F leached out from soil treated by these fertilizers were 0.25% and 0.24%, respectively. However, unanticipated lower leachability of F appeared in compound fertilizer (N:P:K = 17:17:17), nitrogen fertilizer, dipterex, fluoroglycofen, fluopimomide, simulative dry deposition (YF3), and phosphogypsum loaded soils compared with additive-absent treatment. Although phosphogysum had a high F concentration, minimum proportion of F released (0.18%) was observed in phosphogypsum-coverd soil. The amounts of F leaching-out from surface soils (0-25 cm) treated with nitrogen fertilizer decreased 1.03 kg ha-1 comparing with blank control. Soil with phosphate fertilizer leached 5.47 kg F ha-1 a year, having the highest environment risk to deeper soil and groundwater. However, phosphogypsum and dry deposition of airbone F chemical had few effects on F leaching in soil. F-containing materials from agricultural process may leach more F from surface soils than industrial sources.

A novel Biochar modified by Chitosan-Fe/S for tetracycline adsorption and studies on site energy distribution.

A novel wasted sludge-based Biochar modified by Chitosan and Fe/S (BCFe/S) was prepared for tetracycline (TC) removal from water. To investigate the similarities and differences in adsorption behaviors between Biochar and BCFe/S, characterization, kinetics, isotherms and thermodynamics were discussed. The studies on site energy distribution (SED) were also presented. The results showed that the maximum TC adsorption amount was 51.78 mg/g for Biochar, while it was 183.01 mg/g for BCFe/S-4. Meanwhile, electrostatic attraction, π-π stacking, pore filling, silicate bonding and hydrogen bonding were the main adsorption mechanisms for TC removal by Biochar. Besides above mechanisms, chelating and ion exchange were also accounted for adsorption mechanisms for TC uptake by BCFe/S-4. Moreover, SED results revealed that the surface of Biochar was more homogeneous while the surface of BCFe/S-4 was more heterogeneous at higher temperature. Findings of this work could offer valuable information in designing adsorbents and investigating adsorption mechanisms.