Effects of Zr substitution on soot combustion over cubic fluorite-structured nanoceria: Soot-ceria contact and interfacial oxygen evolution

Ceria is widely used as a catalyst for soot combustion, but effects of Zr substitution on the reaction mechanism is ambiguous. The present work elucidates effects of Zr substitution on soot combustion over cubic fluorite-structured nanoceria. The nanostructured CeO₂, Ce_0.92Zr_0.08O₂, and Ce_0.84Zr_0.16O₂ composed of 5–6 nm crystallites display T_m-CO2 (the temperature at maximum CO₂ yield) at 383, 355, and 375°C under 10 vol.% O₂/N₂, respectively. The size of agglomerate decreases from 165.5 to 51.9–57.3 nm, which is beneficial for the soot-ceria contact. Moreover, Zr increases the amount of surface oxygen vacancies, generating more active oxygen (O₂^? and O^?) for soot oxidation. Thus, the activities of Ce_0.92Zr_0.08O₂ and Ce_0.84Zr_0.16O₂ in soot combustion are better than that of CeO₂. Although oxygen vacancies promote the migration of lattice O^2?, the enriched surface Zr also inhibits the mobility of lattice O^2?. Therefore, the T_m-CO2 of Ce_0.84Zr_0.16O₂ is higher than that of Ce_0.92Zr_0.08O₂. Based on reaction kinetic study, soot in direct contact with ceria preferentially decomposes with low activation energy, while the oxidation of isolated soot occurs through diffusion with high activation energy. The obtained findings provide new understanding on the soot combustion over nanoceria.     

Evaluation of the technoeconomic feasibility of electrochemical hydrogen peroxide production for decentralized water treatment

• Gas diffusion electrode (GDE) is a suitable setup for practical water treatment. • Electrochemical H₂O₂ production is an economically competitive technology. • High current efficiency of H₂O₂ production was obtained with GDE at 5–400 mA/cm². • GDE maintained high stability for H₂O₂ production for ~1000 h. • Electro-generation of H₂O₂ enhances ibuprofen removal in an E-peroxone process. This study evaluated the feasibility of electrochemical hydrogen peroxide (H₂O₂) production with gas diffusion electrode (GDE) for decentralized water treatment. Carbon black-polytetrafluoroethylene GDEs were prepared and tested in a continuous flow electrochemical cell for H₂O₂ production from oxygen reduction. Results showed that because of the effective oxygen transfer in GDEs, the electrode maintained high apparent current efficiencies (ACEs,>80%) for H₂O₂ production over a wide current density range of 5–400 mA/cm², and H₂O₂ production rates as high as ~202 mg/h/cm² could be obtained. Long-term stability test showed that the GDE maintained high ACEs (>85%) and low energy consumption (<10 kWh/kg H₂O₂) for H₂O₂ production for 42 d (~1000 h). However, the ACEs then decreased to ~70% in the following 4 days because water flooding of GDE pores considerably impeded oxygen transport at the late stage of the trial. Based on an electrode lifetime of 46 days, the overall cost for H₂O₂ production was estimated to be ~0.88 $/kg H₂O₂, including an electricity cost of 0.61 $/kg and an electrode capital cost of 0.27 $/kg. With a 9 cm² GDE and 40 mA/cm² current density, ~2–4 mg/L of H₂O₂ could be produced on site for the electro-peroxone treatment of a 1.2 m³/d groundwater flow, which considerably enhanced ibuprofen abatement compared with ozonation alone (~43%–59% vs. 7%). These findings suggest that electrochemical H₂O₂ production with GDEs holds great promise for the development of compact treatment technologies for decentralized water treatment at a household and community level.     

Effect of alkaline earth metal promoter on catalytic activity of MnO2 for the complete oxidation of toluene

Herein, Na⁺ and Ca²⁺ are introduced to MnO₂ through cation-exchange method. The presence of Na⁺ and Ca²⁺ significantly enhance the catalytic activity of MnO₂ in toluene oxidation. Among them, the Ca-MnO₂ catalyst exhibits the best catalytic activity (T₅₀ = 194°C, T₉₀ = 215°C, E_a = 57.2 kJ/mol, reaction rate 8.40 × 10^?10 mol/(sec?m²) at 210°C. T₅₀ and T₉₀: the temperature of 50% and 90% toluene conversion; E_a: apparent activation energy) and possess high tolerance against 2.0 vol.% water vapor. Results reveal that the increased acidic sites of the MnO₂ sample can enhance the adsorption of gaseous toluene, and the mobility of oxygen species and the content of reactive oxygen species in the catalyst are significantly improved due to the formed oxygen vacancy. Thus these two factors result in excellent catalytic performance for toluene oxidation combining with the weak CO₂ adsorption ability.     

Oxidative degradation of phenol by sulfidated zero valent iron under aerobic conditions: The effect of oxalate and tripolyphosphate ligands

After adding either organic or inorganic ligands, sulfidated nano-zero-valent iron (SnZVI) was used for aerobic degradation of phenol, and the effect of the ligand species on oxidation performance was investigated. We found that SnZVI hardly degraded phenol in the absence of ligand addition. Ligands initiated and promoted the degradation of pollutants by SnZVI. The data herein show that a characteristic inorganic ligand, tripolyphosphate (TPP), is more effective in enhancing oxidation than a characteristic organic ligand oxalate. In addition to the scavenging of reactive oxidants by the organic ligand, more ferrous ion (Fe(II)) dissolution from SnZVI in the TPP system is another cause for the superior enhancement by the inorganic ligand. In the oxalate system, as the sulfur content of SnZVI increased, the oxidation efficiency increased because FeS shell promoted the transfer of electrons to produce more reactive oxygen species (ROS). In TPP system, the effect of sulfur content on oxidation performance is more complex. The SnZVI with low sulfur content showed poor oxidation performance compared with that of nZVI. Further experiments proved that sulfidation might weaken the complexation of TPP with surface bound Fe, which would slow down the ionic Fe(II) dissolution rate. Therefore, sulfidation has the dual effects of enhancing electron transfer and inhibiting the complexation of inorganic ligands. In addition, the mechanisms of ROS generation in different ligand systems were investigated herein. Results showed that the critical ROS in both the oxalate and TPP systems are hydroxyl radicals, and that they are produced via one-electron activation of O₂.     

Effects of chemical modification on physicochemical properties and adsorption behavior of sludge-based activated carbon

This study aimed to explore the adsorption performance of sludge-based activated carbon (SBC) towards dissolved organic matters (DOMs) removal from sewage, and investigated the modification effect of different types of chemicals on the structure of synthesized SBC. Waste activated sludge (WAS) was used as a carbon source, and HCl, HNO₃, and NaOH were used as different types of chemicals to modify the SBC. With the aid of chemical activation, the modified SBC showed higher adsorption performances on DOMs removal with maximum adsorption of 29.05 mg/g and second-order constant (k) of 0.1367 (L/mol/sec) due to the surface elution of ash and minerals by chemicals. The surface elemental composition of MSBC suggested that the content of C-C and C-O functional groups on the surface of modified sludge-based activated carbon (MSBC) played an important role on the adsorption capacities of MSBC towards DOMs removal in sewage. Additionally, the residual molecular weight of DOMs in sewage was investigated using a 3-dimension fluorescence excitation-emission matrix (3D-EEM) and high-performance size exclusion chromatography (HP-SEC). Results showed that the chemical modification significantly improved the adsorption capacity of MSBC on humic acids (HA) and aromatic proteins (APN), and both of NaOH-MSBC and HCl-MSBC were effective for a wide range of different AMW DOMs removal from sewage, while the HNO₃-MSBC exhibited poorly on AMW organics of 2,617 Da and 409 Da due to the reducing content of macropore. In brief, this study provides reference values for the impact of the chemicals of the activation stage before the SBCs application.     

Using polymer mats to biodegrade atrazine in groundwater: laboratory column experiments

Large-scale column experiments were undertaken to evaluate the potential of in situ polymer mats to deliver oxygen into groundwater to induce biodegradation of the pesticides atrazine, terbutryn and fenamiphos contaminating groundwater in Perth, Western Australia. The polymer mats, composed of woven silicone (dimethylsiloxane) tubes and purged with air, were installed in 2-m-long flow-through soil columns. The polymer mats proved efficient in delivering dissolved oxygen to anaerobic groundwater. Dissolved oxygen concentrations increased from <0.2 mg l(-1) to approximately 4 mg l(-1). Degradation rates of atrazine in oxygenated groundwater were relatively high with a zero-order rate of 240-380 microg l(-1) or a first-order half-life of 0.35 days. Amendment with an additional carbon source showed no significant improvement in biodegradation rates, suggesting that organic carbon was not limiting biodegradation. Atrazine degradation rates estimated in the column experiments were similar to rates determined in laboratory culture experiments, using pure cultures of atrazine-mineralising bacteria. No significant degradation of terbutryn or fenamiphos was observed under the experimental conditions within the time frames of the study. Results from these experiments indicate that remediation of atrazine in a contaminated aquifer may be achievable by delivery of oxygen using an in situ polymer mat system.     

Spatio-temporal dissolved oxygen dynamics in the Orbetello lagoon by fuzzy pattern recognition

This paper models the dissolved oxygen (DO) dynamics in the Orbetello lagoon as a function of the physico-chemical and ecological system variables, including the submerged vegetation, nutrients, and hydrodynamics. It should be viewed as the concluding sequel to a previous paper describing the dynamics of the lagoon ecosystem [Giusti, E., Marsili-Libelli, S., 2006. An integrated model for the Orbetello lagoon ecosystem, Ecol. Model. 196, 379–394] by introducing the missing DO dynamics. The model considers the oxygen demand originating from the decay of carbonaceous and nitrogenous compounds, as well as photosynthesis and natural reaeration by winds and currents as the oxygen producing processes. With a fixed-parameter set the model could accurately reproduce each single circadian DO cycle, but in the long run it failed to extend this fit and could not accommodate the large DO fluctuations induced by the seasonal variability. In order to enhance the model flexibility, a fuzzy pattern recognition algorithm was designed to classify the circadian DO patterns into four typical behaviours, related to the season, and estimate the corresponding parameters, with the overall model output being a fuzzy combination of these sets. The paper discusses several methods to patch the parameter sets and compares their performance in tracking long-term DO variations. A final assessment of the model validity is obtained by incorporating the whole DO dynamics (model, fuzzy pattern recognition and parameter combination) into the general lagoon model and producing a consistently correct series of DO daily distributions over a yearly cycle. Thus the paper contains both a practical and a methodological aspect. The practical one is the linking of all the lagoon dynamics to the dissolved oxygen kinetics in order to clarify to what extent macroalgae and macrophytes influence the oxygen balance. The methodological aspect consists of extending the validity of short-term models to long time-horizons through a patching technique supported by fuzzy pattern recognition.     

有机碳源和溶解氧对亚硝酸盐生物硝化的影响研究

从城市污水处理厂的活性污泥中纯化分离到高活性硝化菌株N-20（Nitrobacter sp．）,在一种新型材料Carbon Foam的表面挂膜;通过对菌株N-20进行摇瓶试验,选择添加有机碳源的种类,将其在pH7．5～8．0、温度28℃的条件下,分别以NaNO2和K2HPO4为氮源和磷源,通过生物滤塔中的液相连续试验,考察在不同DO的条件下有机碳源对硝化作用的影响规律。结果表明,以葡萄糖作为有机碳源,DO≥2mg／L,葡萄糖低于20mg／L时,生物滤塔内可进行正常硝化,NO2^--N的硝化去除率维持在90％左右,随着葡萄糖浓度的增加,硝化去除率下降到70％;DO≤2mg／L,葡萄糖对硝化作用的抑制增强,当葡萄糖为200mg／L时,生物滤塔中NO^2-—N的硝化去除率仅为32％。     

Dibutyl phthalate adsorption characteristics using three common substrates in aqueous solutions

• DBP adsorption was tested using three kinds of substrates in constructed wetlands. • The DBP adsorption capacity followed the order: steel slag>gravel>shell sand. • High temperatures increased the DBP adsorption capacity in the substrates. • DOM consistently inhibited the DBP adsorption onto steel slag and gravel. In recent years, the presence and adverse impacts of phthalic acid esters in aquatic environments have gained increasing attention. This work investigated the adsorption behavior of a typical phthalic acid ester, dibutyl phthalate (DBP), onto steel slag, gravel, and shell sand (substrates commonly used in constructed wetlands). The influence of dissolved organic matter (DOM) on DBP adsorption was investigated using humic acid as a proxy for DOM. The results demonstrated that the adsorption of DBP to three substrates reached equilibrium within 96 h, and the adsorption kinetics were well fitted by a pseudo-second-order model. The DBP adsorption isotherms were best fitted by the Langmuir adsorption model. The DBP adsorption capacity decreased in the order of steel slag>gravel>shell sand, with values of 656 mg/kg, 598 mg/kg, and 6.62 mg/kg at 25°C, respectively. DBP adsorbed to the surface of all substrates in a monolayer via an endothermic process. The DBP adsorption capacities of steel slag and gravel decreased as the DOM content increased. The DBP adsorption mechanisms to steel slag and gravel mainly involved the surface coordination of DBP with –OH or –COOH groups and electrostatic interactions. The results of this work suggest that steel slag and gravel may be ideal substrates for use in constructed wetlands to treat wastewater polluted with DBP.     

Influence of thermal environment on metallographic structure characteristics of the electric arc bead pattern

Electrical apparatuses are prone to arc, which generally causes a fire, even an explosion hazard, when a flammable gas mixture is present, especially during industrial processes. Terrible fire scenes are challenging for fire investigations. In this work, by performing a simultaneous thermal analysis test we simulated a fire environment and found that as the oxygen concentration decreased, the oxidation/exothermic peak temperature of ‘cause’ bead became higher, but the melting temperature was unaffected. Results indicated that the bead pattern underwent oxidation at approximately 831 °C, melting initiated at approximately 1060 °C, and the pattern then disappeared. The melted pattern grain changes were divided into three critical temperature stages: Approximately 600 °C, the onset temperature at which the melted pattern grains began to be equiaxed; approximately 831 °C, at which the grains were interspersed with oxygen-containing material; and 831–1060 °C, when the grains disappeared, which is a criterion for identifying electrical fires. However, the boundaries remained throughout the thermal environment process. Moreover, the bead pattern demonstrated three metallographic regions: Deep layer (Region I), the intermediate layer (Region Ⅱ), and surface layer (Region Ⅲ). Region I was the most thermally sensitive, in which equiaxed crystals first appeared. Region Ⅲ was the thermal reaction lag zone, in which the typical branching crystals finally disappeared, and Region Ⅱ was intermediate between Regions I and Ⅲ. The results may help fire investigators determine the fire scene temperature stages and provide support for fire evidence extraction.