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.     

Green and efficient degradation of cefoperazone sodium by Bi4O5Br2 leading to the production of non-toxic products: Performance and degradation pathway

Photocatalytic process represents a promising approach to overcome the pollution challenge associated with the antibiotics-containing wastewater. This study provides a green, efficient and novel approach to remove cephalosporins, particularly cefoperazone sodium (CFP). Bi₄O₅Br₂ was chosen for the first time to systematically study its degradation for CFP, including the analysis of material structure, degradation performance, the structure and toxicity of the transformation products, etc. The degradation rate results indicated that Bi₄O₅Br₂ had an excellent catalytic activity leading to 78% CFP removal compared with the pure BiOBr (38%) within 120 min of visible light irradiation. In addition, the Bi₄O₅Br₂ presents high stability and good organic carbon removal efficiency. The effects of the solution pH (3.12 - 8.75) on catalytic activity revealed that CFP was mainly photocatalyzed under acidic conditions and hydrolyzed under alkaline conditions. Combined with active species and degradation product identification, the photocatalytic degradation pathways of CFP by Bi₄O₅Br₂ was proposed, including hydrolysis, oxidation, reduction and decarboxylation. Most importantly, the identified products were all hydrolysis rather than oxidation byproducts transformed from the intermediate of β-lactam bond cleavage in CFP molecule, quite different from the mostly previous studies. Furthermore, the final products were demonstrated to be less toxic through the toxicity analysis. Overall, this study illustrates the detailed mechanism of CFP degradation by Bi₄O₅Br₂ and confirms Bi₄O₅Br₂ to be a promising material for the photodegradation of CFP.     

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.     

铝合金化学氧化膜盐雾试验后腐蚀点评定方法研究

目的制定飞机用2024铝合金表面阿洛丁1200S化学氧化膜盐雾试验后腐蚀点的评定依据。方法通过开展铝合金化学氧化膜盐雾试验,分别利用目视、SEM微观、能谱分析和电化学阻抗测试等手段,表征盐雾试验后的腐蚀形貌及特征。结果试验后样品表面出现的典型腐蚀特征尺寸大于或等于0.15 mm时,正常视力的检测人员均能目视可见。目视可见的黑点、典型彗星状拖尾或只有彗星尾巴等形貌处的化学转化膜和基材已腐蚀,局部有腐蚀点的膜层,其耐蚀性大幅下降,失去对侵蚀性介质的阻挡能力。结论仅出现不符合目视可见和基体腐蚀特征,不能判定为腐蚀点。当出现肉眼可见的黑点,典型彗星状拖尾或只有彗星尾巴等形貌,可判定为腐蚀点。在实际生产检验检测过程中,可采取类似方法研究腐蚀点的评判方法,建立铝合金表面处理盐雾试验后腐蚀图谱和腐蚀点评定准则。     

Ag3PO4/g-C3N4复合光催化剂的制备及其可见光催化性能

采用简单的原位沉淀法合成了可见光驱动型光催化剂Ag₃PO₄/g-C₃N₄.利用X-射线衍射（XRD）、傅里叶红外光谱（FT-IR）、扫描电子显微镜（SEM）、X-射线能谱（XPS）以及紫外可见漫反射光谱（UV-Vis DRS）等表征手段对合成的样品进行了表征.与单一的Ag₃PO₄和g-C₃N₄相比,Ag₃PO₄/g-C₃N₄复合材料对左氧氟沙星表现出了更高的催化效率.根据能带分析和自由基捕获试验,提出了Ag₃PO₄/g-C₃N₄复合材料Z型异质结构的作用机制.     

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。     

碳化泡沫负载Co3O4活化过硫酸盐降解罗丹明B

Co₃O₄具有优良的活化过硫酸盐的性能而受到人们的重视,但Co₃O₄粉体易团聚、使用过程中难以分离、易流失和重复利用率差等问题严重制约了其实际应用．通过水热法制备碳化三聚氰胺泡沫负载Co₃O₄非均相催化剂．采用X-射线衍射仪（XRD）和扫描电子显微镜（SEM）对催化剂的结构和表面形貌进行分析．研究不同因素对催化剂活化过硫酸氢钾（PMS）降解罗丹明B（RhB）的性能．其最优催化工艺参数：催化剂投加量为35 mg·L^-1、PMS质量浓度为50 mg·L^-1和pH为7、RhB初始质量浓度为10 mg·L^-1,30 min反应后对RhB降解率为98%．结果表明,增大碳化泡沫负载Co₃O₄非均相催化剂投加量和PMS质量浓度能明显提高对RhB的降解率;而增加RhB初始质量浓度和提高pH值会明显抑制RhB的降解率．催化反应过程符合准一级动力学方程．温度对RhB降...     

MnO2@Fe3O4/石墨烯复合材料对水中Pb(Ⅱ)的吸附

以氧化石墨烯（GO）为原料制备MnO₂@Fe₃O₄/石墨烯（RGO）,考察吸附过程中MnO₂@Fe₃O₄/RGO投加量、溶液pH值、初始浓度和吸附时间等因素对Pb（Ⅱ）的去除率和吸附量的影响,并运用BET比表面积测试法计算MnO₂@Fe₃O₄/RGO的比表面积和平均孔径,采用扫描电子显微镜（SEM）,振动样品磁强计（VSM）,X射线衍射（XRD）和X射线光电子能谱（XPS）等对样品进行表征.结果表明：MnO₂@Fe₃O₄/RGO的比表面积为89.164m²/g,孔容为0.284cm³/g;随着pH值在2~10范围内增加,复合材料对Pb（Ⅱ）的去除率先增大后减小,pH=6时达到最大值.通过4种等温吸附模型（Langmuir、Freundlich、Temkin、D-R模型）和4种吸附动力学模型（伪一级动力学、伪二级动力学、Elovich、颗粒内扩散模型）拟合发现,MnO₂@Fe₃O₄/RGO对Pb（Ⅱ）吸附符合伪二级动力学模型.吸附等温线更符合Langmiur模型,属于典型的单分子层吸附,以化学吸附为主,最大吸附量为265.3mg/g.