Engineering Built-In Electric Field Microenvironment of CQDs/g-C3N4 Heterojunction for Efficient Photocatalytic CO2 Reduction.

Graphitic carbon nitride (CN), as a nonmetallic photocatalyst, has gained considerable attention for its cost-effectiveness and environmentally friendly nature in catalyzing solar-driven CO2 conversion into valuable products. However, the photocatalytic efficiency of CO2 reduction with CN remains low, accompanied by challenges in achieving desirable product selectivity. To address these limitations, a two-step hydrothermal-calcination tandem synthesis strategy is presented, introducing carbon quantum dots (CQDs) into CN and forming ultra-thin CQD/CN nanosheets. The integration of CQDs induces a distinct work function with CN, creating a robust interface electric field after the combination. This electric field facilitates the accumulation of photoelectrons in the CQDs region, providing an abundant source of reduced electrons for the photocatalytic process. Remarkably, the CQD/CN nanosheets exhibit an average CO yield of 120 µmol g-1, showcasing an outstanding CO selectivity of 92.8%. The discovery in the work not only presents an innovative pathway for the development of high-performance photocatalysts grounded in non-metallic CN materials employing CQDs but also opens new avenues for versatile application prospects in environmental protection and sustainable cleaning energy.

Enhanced hydrodechlorination of 4-chlorophenol through carboxymethylcellulose-modified Pd/Fe nanosuspension synthesized by one-step methods.

Palladized iron (Pd/Fe) represents one of the most common modification strategies for nanoscale zero-valent iron (nZVI). Most studies prepared Pd/Fe by reducing iron salts and depositing Pd species on the surface of pre-synthesized nZVI, which can be called the two-step method. In this study, we proposed a one-step method to obtain Pd/Fe by the concurrent formation of Fe0 and Pd0 and investigated the effects of these two methods on 4-chlorophenol (4-CP) removal, with carboxymethylcellulose (CMC) coated as a surface modifier. Results indicated that the one-step method, not only streamlined the synthesis process, but also Pd/Fe-CMCone-step, synthesized by it, exhibited a higher 4-CP removal rate (97.9%) compared to the two-step method material Pd/Fe-CMCtwo-step (82.4%). Electrochemical analyses revealed that the enhanced activity of Pd/Fe-CMCone-step was attributed to its higher electron transfer efficiency and more available reactive species, active adsorbed hydrogen species (Hads*). Detection of intermediate products demonstrated that, under the influence of Pd/Fe-CMCone-step, the main route of 4-CP was through hydrodechlorination (HDC) to form phenol and H* was the main active specie, supported by EPR tests, quenching experiments and product analysis. Additionally, the effects of initial 4-CP concentration, initial pH, O2 concentration, anions such as Cl-, SO42-, HCO3-, and humic acid (HA) were also investigated. In conclusion, the results of this study suggest that Pd/Fe-CMCone-step, synthesized through the one-step method, is a convenient and efficient nZVI-modifying material suitable for the HDC of chlorinated organic compounds.

1D/3D Heterogeneous Assembling Body of Cobalt Nitrides for Highly Efficient Overall Hydrazine Splitting and Supercapacitors.

Herein, the construction of a heterostructured 1D/3D CoN-Co2 N@NF (nickel foam) electrode used for thermodynamically favorable hydrazine oxidation reaction (HzOR), as an alternative to sluggish anodic oxygen evolution reaction (OER) in water splitting for hydrogen production, is reported. The electrode exhibits remarkable catalytic activities, with an onset potential of -0.11 V in HzOR and -71 mV for a current density of 10 mA cm-2 in hydrogen evolution reaction (HER). Consequently, an extraordinary low cell voltage of 53 mV is required to achieve 10 mA cm-2 for overall hydrazine splitting in a two-electrode system, demonstrating significant energy-saving advantages over conventional water splitting. The HzOR proceeds through the 4e- reaction pathway to release N2 while the 1e- pathway to emit NH3 is uncompetitive, as evidenced by differential electrochemical mass spectrometric measurements. The X-ray absorption spectroscopy, in situ Raman spectroscopy, and theoretical calculations identify cobalt nitrides rather than corresponding oxides/(oxy)hydroxides as catalytic species for HzOR and illustrate advantages of heterostructured CoN-Co2 N in optimizing adsorption energies of intermediates/reagents and promoting catalytic activities toward both HzOR and HER. The CoN-Co2 N@NF is also an excellent supercapacitive material, exhibiting an increased specific capacity (938 F g-1 at 1 A g-1 ) with excellent cycling stability (95.8%, 5000 cycles).

ZnS-embedded porous carbon for peroxydisulfate activation: Enhanced electron transfer for bisphenol A degradation.

Transition metal sulfides have garnered increasing attention for their role in persulfate activation, a crucial process in environmental remediation. However, the function of metal sulfides without reversible valence changes, such as ZnS, remains largely unexplored in this context. Here we report ZnS-embedded porous carbon (ZnS-C), synthesized through the pyrolysis of Zn-MOF-74 and dibenzyl disulfide. ZnS-C demonstrates remarkable activity in activating peroxydisulfate (PDS) across a wide pH range, enabling the efficient mineralization removal of bisphenol A (BPA). Through electrochemical investigation and theoretical simulations of charge density distributions, we unveil that the electron transfer from BPA to PDS mediated by the ZnS-C catalyst governs the reaction. This study, both in theory and experiment, demonstrates metal sulfide as electron pump that enhances electron transfer efficiency in PDS activation. These findings redefine the role of metal sulfide catalysts, shedding new light on their potential for regulating reaction pathways in PDS activation processes.

Enhanced anaerobic digestion of human feces by ferrous hydroxyl complex (FHC): Stress factors alleviation and microbial resistance improvement.

Anaerobic digestion (AD) offers a reliable strategy for resource recovery from source-separated human feces (HF), but is limited by a disproportionate carbon/nitrogen (C/N) ratio. Ferrous hydroxyl complex (FHC) was first introduced into the HF-AD system to mediate methanogenesis. Mono-digestion of undiluted HF was inhibited by high levels of volatile fatty acids (VFAs), ammonia, and hydrogen sulfide (H2S). FHC addition at optimum dosage (500-1000 mg/L) increased the cumulative methane (CH4) yield by 22.7%, enhanced the peak value of daily CH4 production by 60.5%, and shortened the lag phase by 24.7%. H2S concentration in biogas was also greatly decreased by FHC via precipitation. FHC mainly facilitated the hydrolysis, acidification, and methanogenesis processes. The production and transformation of VFAs were optimized in the presence of FHC, thus relieving acid stress. FHC elevated the activities of alkaline protease, cellulase, and acetate kinase by 32.3%, 18.2%, and 30.3%, respectively. Microbial analysis revealed that hydrogenotrophic methanogens prevailed in mono-digestion at high HF loading but were weakened after FHC addition. FHC also enriched Methanosarcina, thereby expanding the methanogenesis pathway and improving the resistance to ammonia stress. This work would contribute to improving the methanogenic performance and resource utilization for HF anaerobic digestion.

Self-Assembled Core-Shell Structure MgO@TiO2 as a K2CO3 Support with Superior Performance for Direct Air Capture CO2.

Traditional carbon capture and storage technologies for large point sources can at best slow the rate of increase in atmospheric CO2 concentrations. In contrast, direct capture of CO2 from ambient air, or "direct air capture" (DAC), offers the potential to become a truly carbon-negative technology. Composite solid adsorbents fabricated by impregnating a porous matrix with K2CO3 are promising adsorbents for the adsorption capture of CO2 from ambient air. Nevertheless, the adsorbent can be rapidly deactivated during continuous adsorption/desorption cycles. In this study, MgO-supported, TiO2-stabilized MgO@TiO2 core-shell structures were prepared as supports using a novel self-assembled (SA) method and then impregnated with 50 wt % K2CO3 (K2CO3/MgO@TiO2, denoted as SA-KM@T). The adsorbent exhibits a high CO2 capture capacity of ∼126.6 mg CO2/g sorbent in direct air adsorption and maintained a performance of 20 adsorption/desorption cycles at 300 °C mid-temperature, which was much better than that of K2CO3/MgO. Analysis proved that the core-shell structure of the support effectively inhibited the reaction between the active component (K2CO3) and the main support (MgO) by the addition of TiO2, resulting in higher reactivity, thermal stability, and antiagglomeration properties. This work provides an alternative strategy for DAC applications using adsorbents.

Bias-free driven ion assisted photoelectrochemical system for sustainable wastewater treatment.

Photoelectrochemical (PEC) systems have emerged as a prominent renewable energy-based technology for wastewater treatment, offering sustainable advantages such as eliminating dependence on fossil fuels or grid electricity compared to traditional electrochemical treatment methods. However, previous PEC systems often overlook the potential of ions present in wastewater as an alternative to externally applied bias voltage for enhancing carrier separation efficiency. Here we report a bias-free driven ion assisted photoelectrochemical (IAPEC) system by integration of an electron-ion acceptor cathode, which leverages its fast ion-electron coupling capability to significantly enhance the separation of electrons and holes at the photoanode. We demonstrate that Prussian blue analogues (PBAs) can serve as robust and reversible electron-ion acceptors that provide reaction sites for photoelectron coupling cations, thus driving the hole oxidation to produce strong oxidant free radicals at photoanode. Our IAPEC system exhibits superior degradation performance in wastewater containing chloride medium. This indicates that, in addition to the cations (e.g., Na+) accelerating the electron transfer rate, the presence of Cl- ions further enhance efficient and sustainable wastewater treatment. This work highlights the potential of utilizing abundant sodium chloride in seawater as a cost-effective additive for wastewater treatment, offering crucial insights into the use of local materials for effective, low-carbon, and sustainable treatment processes.

Simultaneous desalination and molecular resource recovery from wastewater using an electrical separation system integrated with a supporting liquid membrane.

Separating molecular substances from wastewater has always been a challenge in wastewater treatment. In this study, we propose a new strategy for simultaneous desalination and selective recovery of molecular resources, by introducing a supported liquid membrane (SLM) with molecular selectivity into an asymmetric flow-electrode capacitive deionization. Salts and molecular substances in wastewater are removed after passing through the ion separation chamber and the molecular separation chamber, respectively. Faradaic reactions, i.e., the electrolysis of water with OH-, occurred in the electrochemical cathode electrode provides a sufficient and continuous chemical potential gradient for the cross-SLM transport of phenol (a model molecule substance). By optimizing the formulation of the liquid membrane and the pore size of the support membrane, we obtained the SLM with the best performance for separating phenol. In continuous experiment tests, the electrochemical membrane system showed stable separation performance and long-term stability for simultaneous salts removal and phenol (sodium phenol) recovery from wastewater. Finally, we demonstrate the potential application of this technology for the recovery of different carbon resources. Overall, the electrochemical system based on SLM is suitable for various wastewater treatment needs and provides a new approach for the recovery of molecular resources in wastewater.

Molecular insight into DOM fate using EEM-PARAFAC and FT-ICR MS and concomitant heavy metal behaviors in biologically treated landfill leachate during coagulation: Al speciation dependence.

Various combined processes with pre-coagulation have been developed for biologically treated landfill leachate, but the microscopic-level processes occurring during coagulation remain largely unknown. Herein, dissolved organic matter (DOM) fate using fluorescence excitation emission matrix spectroscopy combined with parallel factor analysis and electrospray ionization coupled Fourier transform-ion cyclotron resonance mass spectrometry and concomitant heavy metal (HM) behaviors were explored at the molecular level. In addition, AlCl3 and two polyaluminum chloride (PACl) species (dominated by [AlO4Al12(OH)24(H2O)12]7+ and [(AlO4)2Al28(OH)56(H2O)26]18+, respectively) were used. The results show that all coagulants are efficient at removing DOM. PACl was found to be advantageous over AlCl3 in overcoming pH fluctuation, which is ascribed to the different dominant mechanisms, namely, entrapment and sweep flocculation for AlCl3 and charge neutralization for PACl. Consequently, PACl was more effective at removing humic substances, usually high-molecular-weight, oxygen-rich and unsaturated, than protein substances. For HM removal, PACl was likewise better and more stable, where As, Cu, Ni, Co and Hg were removed predominantly via adsorption, and Cr, Zn, Pb, Cd and Mn were removed via coprecipitation. Correlation analysis showed that humic substances tended to complex with HMs and be removed synergistically due to the ubiquitous occurrences of aromatic structures and oxygen-containing functional groups.

Selective abatement of electron-rich organic contaminants by trace complexed Mn(II)-catalyzed periodate via high-valent manganese-oxo species.

Mn(II) is among the most efficient catalysts for the periodate (PI)-based oxidation process. In-situ formed colloidal MnO2 simultaneously serves as the catalyst and oxidant during the degradation of organic contaminants by PI. Here, it is revealed that the complexation of Mn(II) by ethylene diamine tetraacetic acid (EDTA) further enhances the performance of PI-based oxidation in the selective degradation of organic contaminants. As evidenced by methyl phenyl sulfoxide probing, 18O-isotope labeling, and mass spectroscopy, EDTA complexation modulates the reaction pathway between Mn(II) and PI, triggering the generation of high-valent manganese-oxo (MnV-oxo) as the dominant reactive species. PI mediates the single-electron oxidation of Mn(II) to Mn(III), which is stabilized by EDTA complexation and then further oxidized by PI via the oxygen-atom transfer step, ultimately producing the MnV-oxo species. Ligands analogous to EDTA, namely, [S,S]-ethylenediaminedisuccinic acid and L-glutamic acid N,N-diacetic acid, also enhances the Mn(II)/PI process and favors MnV-oxo as the dominant species. This study demonstrates that functional ligands can tune the efficiency and reaction pathways of Mn(II)-catalyzed peroxide and peroxyacid-based oxidation processes.

Electro-enhanced metal-free peroxymonosulfate activator coupled with membrane-assisted process for simultaneous Ni-EDTA decomplexation and Ni ions recovery.

Electro-enhanced metal-free boron/peroxymonosulfate (B/PMS) system has demonstrated potential for efficient metal-organic complexes degradation in an eco-friendly way. However, the efficiency and durability of the boron activator are limited by associated passivation effect. Additionally, the lack of suitable methods utilizing in-situ recovery of metal ions liberated from decomplexation causes huge resource waste. In this study, B/PMS coupled with a customized flow electrolysis membrane (FEM) system is proposed to address above challenges with Ni-EDTA used as the model contaminant. Electrolysis is confirmed to remarkably promote the activation performance of boron towards PMS to efficiently generate •OH which dominated Ni-EDTA decomplexation in the anode chamber. It is revealed that the acidification near the anode electrode improves the stability of boron by inhibiting passivation layer growth. Under optimal parameters (10 mM PMS, 0.5 g/L boron, initial pH = 2.3, current density = 68.87 A/m2), 91.8% of Ni-EDTA could be degraded in 40 min, with a kobs of 6.25 × 10-2 min-1. As the decomplexation proceeds, nickel ions are recovered in the cathode chamber with little interference from the concentration of co-existing cations. These findings provide a promising and sustainable strategy for simultaneous metal-organic complexes removal and metal resources recovery.

Ru(III)-Periodate for High Performance and Selective Degradation of Aqueous Organic Pollutants: Important Role of Ru(V) and Ru(IV).

In this study, Ru(III) ions were utilized to activate periodate (PI) for oxidation of trace organic pollutants (TOPs, e.g., carbamazepine (CBZ)). The Ru(III)/PI system can significantly promote the oxidation of CBZ in a wide initial pH range (3.0-11.0) at 1 µM Ru(III), showing much higher performance than transition metal ions (i.e., Fe(II), Co(II), Zn(II), Fe(III), Cu(II), Ni(II), Mn(II), and Ce(III)) and noble metal ion (i.e., Ag(I), Pd(II), Pt(II), and Ir(III)) activated PI systems. Probe experiments, UV-vis spectra, and X-ray absorption near-edge structure (XANES) spectra confirmed high-valent Ru-oxo species (Ru(V)=O) as the dominant oxidant in the process. Because of the dominant role of Ru(V)=O, the Ru(III)/PI process exhibited a remarkable selectivity and strong anti-interference in the oxidation of TOPs in complex water matrices. The Ru(V)=O species can undertake 1-e- and 2-e- transfer reactions via the catalytic cycles of Ru(V)=O → Ru(IV) → Ru(III) and Ru(V)=O → Ru(III), respectively. The utilization efficiency of PI in the Ru(III)/PI process for the oxidation of TOPs can approach 100% under optimal conditions. PI stoichiometrically transformed into IO3- without production of undesired iodine species (e.g., HOI and I2). This study developed an efficient and environmentally benign advanced oxidation process for rapid removal of TOPs and enriched understandings on reactivity of Ru(V)=O and Ru catalytic cycles.

Pilot-scale study on an advanced Fe-Cu process for refractory wastewater pretreatment.

The extreme pH, high color, and poor biodegradability of refractory wastewater have severe impacts on its biological treatment. To address this issue, an advanced Fe-Cu process with redox reaction and spontaneous coagulation was investigated and applied for pilot-scale (wastewater flow rate of 2000 m3·day-1) pretreatment of separately discharged acidic chemicals and alkaline dyeing wastewater. The advanced Fe-Cu process had five functions: (1) increasing the pH of chemical wastewater to 5.0 and above, with an influent pH of approximately 2.0; (2) transforming refractory organics of chemical wastewater with 10.0% chemical oxygen demand (COD) and 30.8% color removal, thereby enhancing the ratio of biological oxygen demand after five days (BOD5) to COD (B/C) from 0.21 to 0.38; (3) neutralizing the pH of the pretreated chemical wastewater for coagulation application with alkaline dyeing wastewater to avoid adding alkaline chemical; (4) achieving average nascent Fe(II) concentrations of 925.6 mg∙L-1 using Fe-Cu internal electrolysis for mixed wastewater coagulation, resulting in an average of 70.3% color removal and 49.5% COD removal; (5) providing more efficient COD removal and B/C enhancement than FeSO4∙7 H2O coagulation while avoiding secondary pollution. The green process offers an effective, easy-implemented solution for the pretreatment of separately discharged acidic and alkaline refractory wastewater.

Do We Appropriately Detect and Understand Singlet Oxygen Possibly Generated in Advanced Oxidation Processes by Electron Paramagnetic Resonance Spectroscopy?

Electron paramagnetic resonance (EPR) spectroscopy using sterically hindered amine is extensively applied to detect singlet oxygen (1O2) possibly generated in advanced oxidation processes. However, EPR-detectable 1O2 signals were observed in not only the 1O2-dominated hydrogen peroxide (H2O2)/hypochlorite (NaClO) reaction but surprisingly also the 1O2-absent Fe(II)/H2O2, UV/H2O2, and ferrate [Fe(VI)] process with even stronger intensities. By taking advantage of the characteristic reaction between 1O2 and 9,10-diphenyl-anthracene and near-infrared phosphorescent emission of 1O2, 1O2 was excluded in the Fe(II)/H2O2, UV/H2O2, and Fe(VI) process. The false detection of 1O2 was ascribed to the direct oxidation of hindered amine to piperidyl radical by reactive species [e.g., •OH and Fe(VI)/Fe(V)/Fe(IV)] via hydrogen transfer, followed by molecular oxygen addition (forming a piperidylperoxyl radical) and back reaction with piperidyl radical to generate a nitroxide radical, as evidenced by the successful identification of a piperidyl radical intermediate at 100 K and theoretical calculations. Moreover, compared to the highly oxidative species (e.g., •OH and high-valence Fe), the much lower reactivity of 1O2 and the profound nonradiative relaxation of 1O2 in H2O resulted it too selective and inefficient in organic contaminant destruction. This study demonstrated that EPR-based 1O2 detection could be remarkably misled by common oxidative species and thereby jeopardize the understandings on 1O2.

From black water to flushing water: potential applications of chlorine-mediated indirect electrooxidation for ammonia removal.

Removing ammonia from black water is one of the most urgent issues before it can be recycled as flushing water. In this study, an electrochemical oxidation (EO) process with commercial Ti/IrO2-RuO2 anodes to treat black water could remove 100% of different concentrations of ammonia by adjusting the dosage of chloride. Through the relationship between ammonia, chloride, and corresponding the pseudo-first-order degradation rate constant (Kobs), we could determine the chloride dosage and predict the kinetics of ammonia oxidation based on initial ammonia concentration in black water. The optimal N/Cl molar ratio was 1:1.8. The difference between black water and the model solution in terms of ammonia removal efficiency and oxidation products was explored. A higher chloride dosage was beneficial for removing ammonia and shortening the treatment cycle, but it also led to the generation of toxic by-products. Especially HClO and ClO3- generated in black water were 1.2 and 1.5 times more than the synthesized model solution under 40 mA cm-2. Through SEM characterization of electrodes and repeated experiments, the electrodes always maintained a high treatment efficiency. These results demonstrated the potential of the electrochemical process as a treatment method for black water.

Unraveling the effect of CDI electrode characteristics on Cs removal from the perspective of ion transfer and energy composition.

Capacitive deionization (CDI) is surprisingly efficient to remove the aqueous Cs ion due to its small hydrated size and low hydration energy. But current experimental techniques fail in investigating deeply into the influence of some key electrode characteristics due to the difficulty in experimentally fabricating the electrodes as desired. This work presents a dynamic transport model of salt ions in a flow-by CDI cell. By using this model, the electrode thickness, macro- and micro-porosity are investigated to evaluate Cs ion removal efficiency and energy efficiency particularly from the aspect of ion transfer by the approach of decomposing energy contribution. The results indicate that the thick electrode coupled with the high current could greatly improve the effluent quality, but reduce the salt adsorption capacity (SAC). The increasement of the current density from 3 A/m2 to 6 A/m2 greatly decreases the SAC from 4.0 mg/g to 0.8 mg/g. Lower current could prolong the charging period, leading to more ions stored in the micropore. Not all the electrical energy is consumed for separating ions from the feed as desired, but some are used for driving ions diffusing in the electrodes. Consequently charging efficiency will be reduced especially when the electrodes are characterized with high porosity. It is highlighted that future work is required to further consider the complex details of porous structure and pore connectivity.

Dissemination of antibiotic resistance genes through fecal sewage treatment facilities to the ecosystem in rural area.

Infection of antibiotic-resistant pathogens mostly occurs in rural areas. In this paper, the dissemination of antibiotic resistance genes (ARGs) through fecal sewage treatment facilities to the ecosystem in a typical rural area is investigated. Household three-chamber septic tanks (TCs), household biogas digesters (BDs), wastewater treatment plants (WWTPs), vegetable plots, water ponds, etc. Are taken into account. The relative abundance of ARGs in fecal sewage can be reduced by BDs and WWTPs by 80% and 60%, respectively. While TCs show no reduction ability for ARGs. Fast expectation-maximization microbial source tracking (FEAST) analysis revealed that TCs and BDs contribute a considerable percentage (15-22%) of ARGs to the surface water bodies (water ponds) in the rural area. Most ARGs tend to precipitate in the sediments of water bodies and stop moving downstream. Meanwhile, the immigration of microorganisms is more active than that of ARGs. The results provide scientific basic data for the management of fecal sewage and the controlling of ARGs in rural areas.

Highly-efficient molten NaOH-KOH for organochlorine destruction: Performance and mechanism.

Molten salt has been increasingly acknowledged to be useful in the destruction of chlorine-containing organic wastes (COWs), e.g., organochlorine. However, the operational temperatures are usually high, and local structure and thermodynamic property of the molten salt remain largely unclear. In this study, novel molten NaOH-KOH is developed for organochlorine destruction, and its eutectic point can be lowered to 453 K with 1:1 mol ratio of NaOH to KOH. Further experiment shows that this molten NaOH-KOH is highly-efficient towards the destructions of both trichlorobenzene and dichlorophenol, acquiring the final dechlorination efficiencies as 88.2% and 94.1%, respectively. The organochlorine destruction and chloride salt enrichment are verified by fourier-transform infrared spectrometer. Molten NaOH-KOH not only eliminates the C-Cl and CC bonds, but also traps generated CO2, other acidic gases, and possibly particulate matters as a result of the high surface area and high viscosity. This makes it possibly advantageous over incineration for organic waste destruction for carbon neutrality. To sufficiently reveal the inherent mechanism for the temperature dependent performance, molecular dynamics simulation is further adopted. Results show that the radial distance between ions increases with temperature, causing larger molar volume and lower resistance to shear deformation. Moreover, thermal expansion coefficient, specific heat capacity, and ion self-diffusion coefficient of the molten NaOH-KOH are found to increase linearly with temperature. All these microscopic alterations contribute to the organochlorine destruction. This study benefits to develop highly-efficient molten system for COWs treatment via a low-carbon approach.

New insight into the enhanced ozonation of malodorous compounds by Cu(II): Inhibiting the formation of free radicals to promote ozone utilization.

Metal-enhanced ozonation can greatly improve the decay of organic matter; however, whether this method benefits the decay of malodorous compounds or not and the possible mechanism are not well understood. In this study, nine typical malodorous compounds were selected to reveal that Cu(II)-enhanced ozonation can greatly promote the decay of fatty amines because of the direct ozone oxidation, which was enhanced to promote ozone utilization. Moreover, trace Cu(II) can amplify the observed rate constants of dimethylamine and trimethylamine for 48.9% and 155.7%, respectively, and Cu(II) dosage was the determining factor using response surface methodology to investigate the interactions between initial pH, Cu(II) dosage and ozone dosage. These results demonstrated that the formation of •OH and O2•- was inhibited rather than promoted, which was quite different from some previously reported Cu(II)-enhanced ozonation counterparts. Moreover, the enhanced effect of trace Cu(II) was exhibited in both single and complex malodorous compounds. The conversion pathway of nitrogen and sulfur elements was clarified, with the targeted mineralization of nitrogen of nitrogen-containing malodorous compounds into NO3-N and the odor characteristics of sulfur-containing malodorous compounds disappeared. These findings provided new insight for utilizing metal ions to enhance the direct ozone oxidation capacity of malodorous compounds.

An integrated strategy for nutrient harvesting from hydrolyzed human urine as high-purity products: Tracking of precipitation transformation and precise regulation.

The nutrient recovery from source-separated urine is of great significance for a sustainable and closed nutrient loop. However, common urine-processing techniques have several constraints, including inefficient recovery, low product purity and incapability of simultaneously harvesting multiple nutrients. In this study, an integrated strategy of P precipitation and N stripping was first proposed to harvest nutrients from hydrolyzed human urine as high-purity products via precisely regulating Ca/P dosing ratio. Ca(OH)2 was utilized to trigger Ca-P precipitation and elevate pH level. Different from the previously reported conventional struvite method, P recovery was oriented to calcium phosphate. P harvesting behavior was investigated as a function of key factors including initial P concentration and the dosing ratio. A thermodynamic model was constructed to unveil the precipitation transformation mechanism and visualize P recovery for an enhanced controllability. For N harvesting, Ca(OH)2 was dosed to increase the pH of the urine to converts ammonium to ammonia. The resulting ammonia was stripped and then adsorbed by H2SO4 as high-purity ammonium sulfate. Moreover, the sulfate derived from acidification treatment was recovered as calcium sulfate in the interests of material recycling and mitigating secondary contaminations. Results exhibited P recovery efficiency could reach 100 % and purity for calcium phosphate could be above 90 % within a Ca/P ratio range of 1.67-2.0. Further boosting pH to 12, over 85 % of S and 95 % of N was retrieved. The comprehensive scheme provides an efficient approach towards the precise P and N harvesting from hydrolyzed urine and advances the knowledge of precipitation transformation mechanism.