Novel cow dung-doped sludge biochar as an efficient ozone catalyst: Synergy between graphitic structure and defects induces free radical pathways.

A composite material, cow dung-doped sludge biochar (Zn@SBC-CD), was synthesized by one-step pyrolysis using ZnCl2 as an activating agent and applied to a catalytic ozonation process (COP) for methylene blue (MB) removal. SEM, XRD, FTIR, XPS and BET analyses were performed to characterize the biochar (BC) catalysts. Zn@SBC-CD had high graphitization degree, abundant active sites and uniform distribution of Zn on its surface. Complete removal of MB was achieved within 10 min, with a removal rate much higher than that of ozone alone (32.4%), implying the excellent ozone activation performance of Zn@SBC-CD. The influence of experimental parameters on MB removal efficiency was examined. Under the optimum conditions in terms of ozone dose 0.04 mg/mL, catalyst dose 400 mg/L and pH 6.0, COD was completely removed after 20 min. Electron paramagnetic resonance (EPR) analysis revealed radical and non-radical pathways were involved in MB degradation. The Zn@SBC-CD/O3 system generated superoxide anion radicals (•O2-), which were the main active species for MB removal, through adsorption, transformation, and transfer, Furthermore, Zn@SBC-CD exhibited good reusability and stability in cycling experiments. This study provides a novel approach for the utilization of cow dung and sludge in synthesis of functional biocatalysts and application in organic wastewater treatment.

Kinetics and mechanisms of enhanced ammonia abatement under synchronous process of electrochemistry and adsorption.

As a kind of common nitrogen pollutants, ammonia seriously pollutes water and soil environments and threatens human health. The treatment of water contaminated with ammonia was carried out in an electrochemical-adsorption system (ECAS). This paper discusses the capacity, kinetics, and mechanism of ammonia electrosorption, which is accurately described by a pseudo-first-order model, indicating that physical adsorption is the dominating mechanism. A high adsorption capacity of 4.086 mg N/g was attributed to the formation of a large number of adsorption sites and the highly acidic nature of dealumination of zeolites during electrolysis. Fast directional migration of ammonia in the electric field weakened the negative effect of boundary layer on adsorption and accelerated adsorption procedure. Brunauer, Emmett, and Teller measurements and scanning electron microscopy indicated that the formation of new channels and surface erosion, which resulted in a large surface area and pore volume of zeolites and a low resistance towards ion migration. As a whole, this study achieved efficient ammonia removal without the addition of chemical reagents to avoid secondary pollution.

Distribution and removal pathways of heavy metals during the operation of sludge treatment wetlands.

ABSTRACTThe distribution and removal pathways of heavy metals within different sludge treatment wetlands (STWs) during different running periods in Northeast China have not been well studied. In this study, we examined three STWs, i.e. an STW with aeration tubes only (unit 1; U1), an STW with reeds and aeration tubes (unit 2; U2), and an STW with reeds only (unit 3; U3). The results showed that the levels of Cu as well as Zn accumulated faster within STW residual sludge, whereas the levels of Cd, Cr, Ni, and Pb accumulated more slowly and decreased slightly over time. The removal rates of heavy metals from the influent sludge by STWs ranged from 64.5% (Cr) to 92.2% (Zn). Reeds removed heavy metals from the STWs by direct absorption, and Zn was highly enriched in the reeds. The presence of reeds also promoted the spreading of heavy metals to the substrate layer and improved the removal of heavy metals in STWs. The mass of each heavy metal accumulated within the residual sludge of U2 and U3 was lower than that of U1, indicating that reeds could facilitate the removal of heavy metals. The STWs removed heavy metal mainly by substrate adsorption, and the mass percentage of heavy metals accumulated in the substrate ranged from 35.8 to 63.6%.

Electrochemical oxidation of aniline using Ti/RuO2-SnO2 and Ti/RuO2-IrO2 as anode.

Electrocatalytic properties of anode and the electrolyte composition are important parameters influence the degradation efficiency for aniline wastewater. Ti/RuO2-SnO2 and Ti/RuO2-IrO2 have been fabricated using thermal decomposition method and experiments in electrolyte containing 0.05 M Na2SO4, 0.05 M NaCl and 0.05 M Na2SO4+0.005 M FeSO4 at different current density were conducted to study the influence on aniline degradation. Linear sweep voltammetry (LSV) showed that Ti/RuO2-SnO2 had higher oxygen evolution potential and degrade aniline through electrochemical transformation and electrochemical combustion while Ti/RuO2-IrO2 degrade aniline mainly through electrochemical transformation. The study showed that Ti/RuO2-SnO2 had higher electrocatalytic activity towards the degradation of aniline than Ti/RuO2-IrO2 anode in 0.05 M Na2SO4 and in 0.05 M NaCl electrolyte. The maximum TOC removal efficiency for Ti/RuO2-SnO2 was 64.2% at 40 mA cm-2 in Na2SO4 electrolyte while the average MCE was 1.6% and the average ECTOC was 1.51 kWh (g TOC)-1. On the contrary, the maximum TOC removal efficiency for Ti/RuO2-IrO2 was 63.1% at 40 mA cm-2 in NaCl electrolyte while the average MCE was 1.6% and the average ECTOC was 1.95 kWh (g TOC)-1. The presence of Fe2+ in Na2SO4 electrolyte would decrease the TOC removal efficiency except at low current density (20 mA cm-2) for Ti/RuO2-SnO2. These results indicated that Ti/RuO2-SnO2 and Ti/RuO2-IrO2 anode were suitable in Na2SO4 and NaCl electrolyte, respectively, while the presence of Fe2+ would inhibit aniline degradation.

Electrochemical reduction of nitrate on boron-doped diamond electrodes: Effects of surface termination and boron-doping level.

This study is among the first to systematically study the electrochemical reduction of nitrate on boron-doped diamond (BDD) films with different surface terminations and boron-doping levels. The highest nitrate reduction efficiency was 48% and the highest selectivity in the production of nitrogen gas was 44.5%, which were achieved using a BDD electrode with a hydrogen-terminated surface and a B/C ratio of 1.0%. C-H bonds served as the anchor points for attracting NO3- anions close to the electrode surface, and thus accelerating the formation of NO3-(ads). Compared to oxygen termination, hydrogen-terminated BDD exhibited higher electrochemical reactivity for reducing nitrate, resulting from the formation of shallow acceptor states and small interfacial band bending. The hydrophobicity of the hydrogen-terminated BDD inhibited water electrolysis and the subsequent adsorption of atomic hydrogen, leading to increased selectivity in the production of nitrogen gas. A BDD electrode with a boron-doping level of 1.0% increased the density of acceptor states, thereby enhancing the conductivity and promoting the formation of C-H bonds after the cathodic reduction pretreatment leading to the direct reduction of nitrate.

Review on electrochemical system for landfill leachate treatment: Performance, mechanism, application, shortcoming, and improvement scheme.

Landfill leachate is a type of complex organic wastewater, which can easily cause serious negative impacts on the human health and ecological environment if disposed improperly. Electrochemical technology provides an efficient approach to effectively reduce the pollutants in landfill leachate. In this review, the electrochemical standalone processes (electrochemical oxidation, electrochemical reduction, electro-coagulation, electro-Fenton process, three-dimensional electrode process, and ion exchange membrane electrochemical process) and the electrochemical integrated processes (electrochemical-advanced oxidation process (AOP) and biological electrochemical process) for landfill leachate treatment are summarized, which include the performance, mechanism, application, existing problems, and improvement schemes such as cost-effectiveness. The main objective of this review is to help researchers understand the characteristics of electrochemical treatment of landfill leachate and to provide a useful reference for the design of the process and reactor for the harmless treatment of landfill leachate.

Research on complexation ability, aromaticity, mobility and cytotoxicity of humic-like substances during degradation process by electrochemical oxidation.

The humic-like substances were the main organic components in most wastewater (e.g. domestic sewage, toilet wastewater and landfill leachate). Two types of actual humic-like substances (fulvic acid (FA) and biologically treated landfill leachate (BTLL)) were selected to describe the changes in the properties of humic-like substances (complexation ability, aromaticity and mobility) during electrochemical oxidation. Meanwhile, the acute cytotoxicity of FA and BTLL was also tested by acute toxicological test of luminescent bacteria. The results showed that the consumption of coordinating groups such as phenolic groups and hydrogen bonds reduced the complexation ability of FA and BTLL. The functional groups were degraded with the removal order of quinone group, phenolic group and aromatic group, and finally realized the molecular saturation and aromaticity decrease for humic-like substances. The mobility of FA and BTLL was decreased because of the enhancement of hydrophobicity during electrolysis process. Furthermore, the available chlorine produced during electrochemical oxidation was the main acute cytotoxicity substance, therefore, it is necessary to remove it before discharge in order to reduce ecological risks. This study provides a basis for understanding and evaluating the electrochemical degradation process of humic-like substances in detail.

Degradation of nitrogen-containing refractory organic wastewater using a novel alternating-anode electrochemical system.

This study presented a novel alternating-anode electrochemical system (AAES) based on single electrolytic cell for the treatment of nitrogen-containing refractory organic wastewater (NOW). The core of AAES lies in the alternating working of iron anode and DSA anode to integrate different electrochemical processes. The biologically treated landfill leachate (BTLL) was selected as a practical NOW for assessing the performance of AAES. The results indicated that after 140 min of electrolytic reaction, the removal efficiency of chemical oxygen demand and total nitrogen (TN) using AAES was found to be 76.9 and 98.9%, respectively. The main component of dissolved organic matter (DOM) in BTLL included humic-like substances, which could be degraded into small-molecule DOM, such as fulvic-like substances and protein-like substances, by available chlorine and hydroxyl radicals present in AAES. Cathode reduction (NOx--N → NH4+-N and N2) under iron anode and indirect oxidation (NH4+-N → N2) under DSA anode were the main pathways to remove TN from NOW. Owing to the redox conditions created by the alternating anodes, the main stable crystalline forms of precipitates obtained from AAES were Fe3O4 and γ-Fe2O3, which could be separated by using the external magnetic field. The findings of this study may provide a feasible solution for the advanced electrochemical treatment of NOW in a single electrolytic cell as well as rapid separation of precipitates.

Comparison of performance between boron-doped diamond and copper electrodes for selective nitrogen gas formation by the electrochemical reduction of nitrate.

The electrochemical nitrate reduction by using boron-doped diamond (BDD) and copper (Cu) electrodes was investigated at various potentials. Product selectivity of nitrate reduction was strongly dependent on the applied potential for both electrodes. The highest selectivity of nitrogen gas production was obtained at -2.0 V (vs. Ag/AgCl) by using a BDD electrode with a faradaic efficiency as high as 45.2%. Compared with Cu electrode, nitrate reduction on BDD electrode occurred at more positive potential, and the production of nitrogen gas was larger. The transformation of surface-adsorbed nitrate into molecular nitrogen would be accelerated on BDD electrode with hindering nitrite production. In addition, low concentration of surface-adsorbed hydrogen on the BDD would also retard the ammonia generation, leading to increase in the selectivity of nitrogen gas formation. Meanwhile, BDD electrode could hinder the hydrogen evolution reaction, which enhanced the efficiency for nitrate reduction and decreased energy consumption. BDD electrode has excellent stability to remain better performance for reducing nitrate during electrolysis without any variation of surface morphology or chemical components.

Research on the treatment of biologically treated landfill leachate by joint electrochemical system.

Biologically treated landfill leachate (BTLL) is typically characterized by significantly high amount of total nitrogen (TN) and chemical oxygen demand (COD), and it has low biodegradability. In this study, a joint electrochemical system (JES) composed of iron anode reactor (IAR) and Ti/RuO2 anode reactor (TAR) was constructed to remove both TN and COD from BTLL and improve its biodegradability. The IAR and TAR with the same structure but using different anodes. As a result, JES could simultaneously remove COD and TN by 90.9 ±â€¯0.3% and 90.2 ±â€¯1.0%, respectively. Reduction of nitrite-N by Cu/Zn cathode in IAR and oxidation of ammonium-N by active chlorine in TAR were the major pathways for TN removal, while the COD could be removed by coagulation of iron flocs and oxidation by hydroxyl radicals and active chlorine. Fluorescence spectrum and parallel factor analysis showed that the main components of organics in BTLL were humic-like substances, fulvic-like substances, and soluble microbial degradation products. Humic-like substances were particularly removed by JES, and the remaining organics after electrolysis were some alkanes (e.g., heptane and nonane). Furthermore, decrease in molecular weight and aromaticity and increase in biodegradable substances indicated that the biodegradability of BTLL was effectively improved by the JES. The developed JES is a promising approach for application in the BTLL treatment.