Efficient degradation of Rhodamine B by magnetically recoverable Fe3O4-modified ternary CoFeCu-layered double hydroxides via activating peroxymonosulfate

Environment-friendly nano-catalysts capable of activating peroxymonosulfate (PMS) have received increasing attention recently. Nevertheless, traditional nano-catalysts are generally well dispersed and difficult to be separated from reaction system, so it is particularly important to develop nano-catalysts with both good catalytic activity and excellent recycling efficiency. In this work, magnetically recoverable Fe₃O₄-modified ternary CoFeCu-layered double hydroxides (Fe₃O₄/CoFeCu-LDHs) was prepared by a simple co-precipitation method and initially applied to activate PMS for the degradation of Rhodamine B (RhB). X-ray diffraction (XRD), fourier transform infrared spectrometer (FT-IR), scanning electron microscope (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller method (BET), and vibrating sample magnetometer (VSM) were applied to characterize morphology, structure, specific surface area and magnetism. In addition, the effects of several key parameters were evaluated. The Fe₃O₄/CoFeCu-LDHs exhibited high catalytic activity, and RhB degradation efficiency could reach 100% within 20 min by adding 0.2 g/L of catalyst and 1 mmol/L of PMS into 50 mg/L of RhB solution under a wide pH condition (3.0-7.0). Notably, the Fe₃O₄/CoFeCu-LDHs showed good super-paramagnetism and excellent stability, which could be effectively and quickly recovered under magnetic condition, and the degradation efficiency after ten cycles could still maintain 98.95%. Both radicals quenching tests and electron spin resonance (ESR) identified both HO? and SO₄^?? were involved and SO₄^?? played a dominant role on the RhB degradation. Finally, the chemical states of the sample's surface elements were measured by X-ray photoelectron spectroscopy (XPS), and the possible activation mechanism in Fe₃O₄/CoFeCu-LDHs/PMS system was proposed according to comprehensive analysis.     

Comparing dark- and photo-Fenton-like degradation of emerging pollutant over photo-switchable Bi2WO6/CuFe2O4: Investigation on dominant reactive oxidation species

The extensive use of tetracycline hydrochloride (TCH) poses a threat to human health and the aquatic environment. Here, magnetic p-n Bi₂WO₆/CuFe₂O₄ catalyst was fabricated to efficiently remove TCH. The obtained Bi₂WO₆/CuFe₂O₄ exhibited 92.1% TCH degradation efficiency and 50.7% and 35.1% mineralization performance for TCH and raw secondary effluent from a wastewater treatment plant in a photo-Fenton-like system, respectively. The remarkable performance was attributed to the fact that photogenerated electrons accelerated the Fe(III)/Fe(II) and Cu(II)/Cu(I) conversion for the Fenton-like reaction between Fe(II)/Cu(I) and H₂O₂, thereby generating abundant ?OH for pollutant oxidation. Various environmental factors including H₂O₂ concentration, initial pH, catalyst dosage, TCH concentration and inorganic ions were explored. The reactive oxidation species (ROS) quenching results and electron spin resonance (ESR) spectra confirmed that ?O₂^? and ?OH were responsible for the dark and photo-Fenton-like systems, respectively. The degradation mechanisms and pathways of TCH were proposed, and the toxicity of products was evaluated. This work contributes a highly efficient and environmentally friendly catalyst and provides a clear mechanistic explanation for the removal of antibiotic pollutants in environmental remediation.     

Marine aquaculture regulates dissimilatory nitrate reduction processes in a typical semi-enclosed bay of southeastern China

Marine aquaculture in semi-enclosed bays can significantly influence nutrient cycling in coastal ecosystems. However, the impact of marine aquaculture on the dynamics of dissimilatory nitrate reduction processes (DNRPs) and the fate of reactive nitrogen remain poorly understood. In this study, the rates of DNRPs and the abundances of related functional genes were investigated in aquaculture and non-aquaculture areas. The results showed that marine aquaculture significantly increased the denitrification (DNF) and dissimilatory nitrate reduction to ammonium (DNRA) rates and decreased the rate of anaerobic ammonium oxidation (ANA), as compared with non-aquaculture sites. DNF was the dominant pathway contributing to the total nitrate reduction, and its contribution to the total nitrate reduction significantly increased from 66.72% at non-aquaculture sites to 78.50% at aquaculture sites. Marine aquaculture can significantly affect the physicochemical characteristics of sediment and the abundances of related functional genes, leading to variations in the nitrate reduction rates. Although nitrate removal rates increased in the marine aquaculture area, ammonification rates and the nitrogen retention index in the aquaculture areas were 2.19 and 1.24 times, respectively, higher than those at non-aquaculture sites. Net reactive nitrogen retention exceeded nitrogen removal in the aquaculture area, and the retained reactive nitrogen could diffuse with the tidal current to the entire bay, thereby aggravating N pollution in the entire study area. These results show that marine aquaculture is the dominant source of nitrogen pollution in semi-enclosed bays. This study can provide insights into nitrogen pollution control in semi-enclosed bays with well-developed marine aquaculture.     

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.     

Identification of close relationship between atmospheric oxidation and ozone formation regimes in a photochemically active region

Understanding ozone (O₃) formation regime is a prerequisite in formulating an effective O₃ pollution control strategy. Photochemical indicator is a simple and direct method in identifying O₃ formation regimes. Most used indicators are derived from observations, whereas the role of atmospheric oxidation is not in consideration, which is the core driver of O₃ formation. Thus, it may impact accuracy in signaling O₃ formation regimes. In this study, an advanced three-dimensional numerical modeling system was used to investigate the relationship between atmospheric oxidation and O₃ formation regimes during a long-lasting O₃ exceedance event in September 2017 over the Pearl River Delta (PRD) of China. We discovered a clear relationship between atmospheric oxidative capacity and O₃ formation regime. Over eastern PRD, O₃ formation was mainly in a NO_x-limited regime when HO₂/OH ratio was higher than 11, while in a VOC-limited regime when the ratio was lower than 9.5. Over central and western PRD, an HO₂/OH ratio higher than 5 and lower than 2 was indicative of NO_x-limited and VOC-limited regime, respectively. Physical contribution, including horizontal transport and vertical transport, may pose uncertainties on the indication of O₃ formation regime by HO₂/OH ratio. In comparison with other commonly used photochemical indicators, HO₂/OH ratio had the best performance in differentiating O₃ formation regimes. This study highlighted the necessities in using an atmospheric oxidative capacity-based indicator to infer O₃ formation regime, and underscored the importance of characterizing behaviors of radicals to gain insight in atmospheric processes leading to O₃ pollution over a photochemically active region.     

高浓度硫化染料染色废水的处理与综合利用

采用混凝气浮－内电解－接触氧化组合工艺处理高浓度硫化染料染色废水，生产运行结果表明：S^2-、COD、BOD5和色度的去除率分别为近100％、94％左右、92．5％－94．8％、96％－100％，处理后出水的各项污染指标均符合国家排放标准，并且实现了部分回用。该处理工艺设备简单、系统运行稳定、投资少、操作方便，具有一定的推广应用价值。     

厌氧氨氧化颗粒污泥快速培养及其抑制动力学

为实现厌氧氨氧化颗粒污泥(ANAMMOX granular sludge,AGS)的快速培养,采用上流式厌氧污泥床(up-flow anaerobic sludge bed,UASB)工艺,在添加少量絮状厌氧氨氧化污泥(flocculent ANAMMOX sludge,FAS)的反应器内填充生物流离球作为填料,对ANAMMOX的启动及FAS的颗粒化进行研究.同时利用Haldane模型研究AGS的基质抑制动力学特性.结果表明,利用生物流离球作为填料,实现了ANAMMOX的启动,总氮去除率达85%以上,总氮容积负荷为0. 72 kg·(m3·d)-1,并在127 d内成功培养出直径1. 0～3. 0 mm的AGS.动力学研究表明,反应器内AGS对氨和亚硝酸盐的最大反应速率分别为1. 46 kg·(kg·d)-1和1. 76 kg·(kg·d)-1,半抑制速率分别是852. 2 mmol·L-1和108. 2 mmol·L-1.与絮状污泥相比,AGS能承受更高的氨和亚硝酸盐抑制浓度,并保持较高的反应速率.采用含有海绵的生物流离球作为填料,能有效加速反应器的启动,加快AGS的形成,对厌氧氨氧化工艺的实际运行具有积极的意义.     

电化学氧化预处理垃圾渗滤液的可行性研究

文章采用电化学氧化技术预处理渗滤液,在以钛涂钌铱为阳极、不锈钢为阴极,极板距离1.5cm,电流密度60mA/cm2,不外加电解质的情况下,电解120min,渗滤液的COD去除率达到48.6%,NH4+离子浓度去除率达53.6%,BOD5/COD比值由0.15提高到0.38,达到了较好的预处理效果。     

Fenton试剂加硫酸处理高浓度含酚废水的研究

研究了硫酸、Fenton试剂对酚的催化降解作用，证实了硫酸与Fenton试剂对酚的催化降解具有协同作用。H_2SO_4－Fenton试剂对高浓度含酚废水的处理结果说明，在Fenton试剂中加入硫酸可大大增加其对酚的降解能力。与单独的Fenton试剂法比较，当H_2O_2∶COD（重量比）＜0．8时，本法对COD≥14000mg／L含酚废水COD去除率可提高40％以上，对高浓度含酚废水具有很好的处理效果。     

Acid Orange 7 degradation using methane as the sole carbon source and electron donor

• AO7 degradation was coupled with anaerobic methane oxidation. • Higher concentration of AO7 inhibited the degradation. • The maximum removal rate of AO7 reached 280 mg/(L·d) in HfMBR. • ANME-2d dominated the microbial community in both batch reactor and HfMBR. • ANME-2d alone or synergistic with the partner bacteria played a significant role. Azo dyes are widely applied in the textile industry but are not entirely consumed during the dyeing process and can thus be discharged to the environment in wastewater. However, azo dyes can be degraded using various electron donors, and in this paper, Acid Orange 7 (AO7) degradation performance is investigated using methane (CH₄) as the sole electron donor. Methane has multiple sources and is readily available and inexpensive. Experiments using ¹³C-labeled isotopes showed that AO7 degradation was coupled with anaerobic oxidation of methane (AOM) and, subsequently, affected by the initial concentrations of AO7. Higher concentrations of AO7 could inhibit the activity of microorganisms, which was confirmed by the long-term performance of AO7 degradation, with maximum removal rates of 8.94 mg/(L·d) in a batch reactor and 280 mg/(L·d) in a hollow fiber membrane bioreactor (HfMBR). High-throughput sequencing using 16S rRNA genes showed that Candidatus Methanoperedens, affiliated to ANME-2d, dominated the microbial community in the batch reactor and HfMBR. Additionally, the relative abundance of Proteobacteria bacteria (Phenylobacterium, Pseudomonas, and Geothermobacter) improved after AO7 degradation. This outcome suggested that ANME-2d alone, or acting synergistically with partner bacteria, played a key role in the process of AO7 degradation coupled with AOM.