Effect of NOx and SO2 on the photooxidation of methylglyoxal: Implications in secondary aerosol formation

Methylglyoxal(CH_3COCHO,MG),which is one of the most abundant α-dicarbonyl compounds in the atmosphere,has been reported as a major source of secondary organic aerosol(SOA).In this work,the reaction of MG with hydroxyl radicals was studied in a 500 L smog chamber at(293±3) K,atmospheric pressure,(18±2)% relative humidity,and under different NOx and SO_2.Particle size distribution was measured by using a scanning mobility particle sizer(SMPS) and the results showed that the addition of SO_2 can promote SOA formation,while different NOx concentrations have different influences on SOA production.High NOx suppressed the SOA formation,whereas the particle mass concentration,particle number concentration and particle geometric mean diameter increased with the increasing NOx concentration at low NOx concentration in the presence of SO_2.In addition,the products of the OH-initiated oxidation of MG and the functional groups of the particle phase in the MG/OH/SO_2 and MG/OH/NOx/SO_2 reaction systems were detected by gas chromatography mass spectrometry(GC-MS) and attenuated total reflection fourier transformed infrared spectroscopy(ATR-FTIR) analysis.Two products,glyoxylic acid and oxalic acid,were detected by GC-MS.The mechanism of the reaction of MG and OH radicals that follows two main pathways,H atom abstraction and hydration,is proposed.Evidence is provided for the formation of organic nitrates and organic sulfate in particle phase from IR spectra.Incorporation of NOx and SO_2 influence suggested that SOA formation from anthropogenic hydrocarbons may be more efficient in polluted environment.     

The study of biological activity of transformation products of diclofenac and its interaction with chlorogenic acid

In the present work we compared the biological activity of DCF, 4′-OHDCF and 5-OHDCF as molecules of most biodegradation pathways of DCF and selected transformation products (2-hydroxyphenylacetic acid; 2,5-dihydroxyphenylacetic acid and 2,6-dichloroaniline) which are produced during AOPs, such as ozonation and UV/H₂O₂. We also examined the interaction of DCF with chlorogenic acid (CGA). CGA is commonly used in human diet and entering the environment along with waste mainly from the processing and brewing of coffee and it can be toxic for microorganisms included in activated sludge. In the present experiment the evaluation of following parameters was performed: E. coli K-12 cells viability, growth inhibition of E. coli K-12 culture, LC₅₀ and mortality of Chironomus aprilinus, genotoxicity, sodA promoter induction and ROS generation. In addition the reactivity of E. coli SM recA:luxCDABE biosensor strain in wastewater matrices was measured. The results showed the influence of DCF, 4′-OHDCF and 5-OHDCF on E. coli K-12 cells viability and bacteria growth, comparable to AOPs by-products. The highest toxicity was observed for selected, tested AOPs by-products, in comparison to the DCF, 4′-OHDCF and 5-OHDCF. Genotoxicity assay indicated that 2,6-dichloroaniline (AOPs by-product) had the highest toxic effect. The oxidative stress assays revealed that the highest level of ROS generation and sodA promoter induction were obtained for DCF, 4′-OHDCF and 5-OHDCF, compared to other tested compounds. We have also found that there is an interaction between chlorogenic acid and DCF, which resulted in increased toxicity of the mixture of the both compounds to E. coli K-12, comparable to parent chemicals. The strongest response of E. coli SM biosensor strain with recA:luxCDABE genetic construct in filtered treated wastewaters, comparable to control sample was noticed. It indicates, that E. coli SM recA:luxCDABE biosensor strains is a good tool for bacteria monitoring in wastewater environment. Due to toxicity and biological activity of tested DCF transformation products, there is a need to use additional wastewater treatment systems for wastewater contaminated with pharmaceutical residues.     

Recent advances in catalytic decomposition of ozone

Ozone (O₃), as a harmful air pollutant, has been of wide concern. Safe, efficient, and economical O₃ removal methods urgently need to be developed. Catalytic decomposition is the most promising method for O₃ removal, especially at room temperature or even subzero temperatures. Great efforts have been made to develop high-efficiency catalysts for O₃ decomposition that can operate at low temperatures, high space velocity and high humidity. First, this review describes the general reaction mechanism of O₃ decomposition on noble metal and transition metal oxide catalysts. Then, progress on the O₃ decomposition performance of various catalysts in the past 30 years is summarized in detail. The main focus is the O₃ decomposition performance of manganese oxides, which are divided into supported manganese oxides and non-supported manganese oxides. Methods to improve the activity, stability, and humidity resistance of manganese oxide catalysts for O₃ decomposition are also summarized. The deactivation mechanisms of manganese oxides under dry and humid conditions are discussed. The O₃ decomposition performance of monolithic catalysts is also summarized from the perspective of industrial applications. Finally, the future development directions and prospects of O₃ catalytic decomposition technology are put forward.     

Effects of calcination temperature on physicochemical property and activity of CuSO4/TiO2 ammonia-selective catalytic reduction catalysts

CuSO_4/TiO_2 catalysts with high catalytic activity and excellent resistant to SO_2 and H_2 O,were thought to be promising catalysts used in Selective catalytic reduction of nitrogen oxides by NH_3.The performance of catalysts is largely affected by calcination temperature.Here,effects of calcination temperature on physicochemical property and catalytic activity of CuSO_4/TiO_2 catalysts were investigated in depth.Catalyst samples calcined at different temperatures were prepared first and then physicochemical properties of the catalyst were characterized by N2 adsorption-desorption,X-ray diffraction,thermogravimetric analysis,Raman spectra,Fourier-transform infrared spectroscopy,X-ray photoelectron spectroscopy,temperature-pro grammed desorption of NH_3,temperature-programmed reduction of H_2 and in situ diffuse reflectance infrared Fourier transform spectroscopy.Results revealed that high calcination temperature had three main effects on the catalyst.First,sintering and anatase transform into rutile with increase of calcination temperature,causing a decrement of specific surface area.Second,decomposition of CuSO_4 under higher calcination temperature,resulting in disappears of Br(?)nsted acid sites(S-OH),which had an adverse effect on surface acidity.Third,CuO from the decomposition of CuSO_4 changed surface reducibility of the catalyst and favored the process of NH_3 oxidation to nitrogen oxides(NO_x).Thus,catalytic activity of the catalyst calcined under high temperatures(≥600℃) decreased largely.     

Synergistic effects of Cu species and acidity of Cu-ZSM-5 on catalytic performance for selective catalytic oxidation of n-butylamine

In this work, a series of Cu-ZSM-5 catalysts with different SiO₂/Al₂O₃ ratios (25, 50, 100 and 200) were synthesized and investigated in n-butylamine catalytic degradation. The n-butylamine can be completely catalytic degradation at 350°C over all Cu-ZSM-5 catalysts. Moreover, Cu-ZSM-5 (25) exhibited the highest selectivity to N₂, exceeding 90% at 350°C. These samples were investigated in detail by several characterizations to illuminate the dependence of the catalytic performance on redox properties, Cu species, and acidity. The characterization results proved that the redox properties and chemisorption oxygen primarily affect n-butylamine conversion. N₂ selectivity was impacted by the Brønsted acidity and the isolated Cu²⁺ species. Meanwhile, the surface acid sites over Cu-ZSM-5 catalysts could influence the formation of Cu species. Furthermore, in situ diffuse reflectance infrared Fourier transform spectra was adopted to explore the reaction mechanism. The Cu-ZSM-5 catalysts are the most prospective catalysts for nitrogen-containing volatile organic compounds removal, and the results in this study could provide new insights into catalysts design for VOC catalytic oxidation.     

基于边介数的省域生态廊道构建方法优化

我国城市建设和生态保护工作均对土地资源有大量需求,二者之间的矛盾在经济优先发展区表现尤为明显.为了有效地改善生态环境,管控土地利用并引导其变化发展,需要建设具备不可替代特征的省域生态廊道.最小累积阻力模型（minimum cumulative resistance,MCR）是识别生态廊道最常用、有效的模型,但在应用于省域尺度时,MCR模型识别的潜在廊道路由存在冗余的问题.因此,通过引入网络科学中的边介数指数（edge-betweenness）对MCR模型进行优化,计算潜在廊道路由的边介数指数值,选取出其中最为重要和简明的结构来连通生态源地,即提取潜在路由中的骨干路由（backbone route）和关键战略点（key strategic point）作为不可替代的结构来指导省域生态廊道建设.将优化后的MCR模型应用于广东省,构建了全长5 493 km的省域生态廊道,其中包含生态源地20处,关键战略点11个,骨干生态廊道29条.骨干路由与关键战略点构成的不可替代省域生态廊道（irreplaceable provincial corridor）能够实现"廊道数量和占地面积最少、连通性基本不变"的目标.研究显示,边介数能够对潜在路由进行优化筛选,识别出维护省域生态安全的关键结构;不可替代生态廊道能够指导省域生态规划和土地空间的发展利用,并为更高水平的生态安全环境提供了演进的基础;同时也为土地资源紧张的地区提供了建设生态廊道的参考与依据.      

轻质高强多功能点阵夹层结构研究进展

根据材料类型和点阵结构,对点阵夹层结构进行了分类简述,并从静态、动态力学性能上,分析了各类点阵夹层结构的优缺点。简要叙述了设计过程中,综合考虑材料、结构以及功能等影响因素,针对不同使用工况的要求,可对各影响因素进行匹配设计,以实现传热特性、电磁波屏蔽特性、声学特性等不同的功能性需求。然后介绍了复合点阵夹层结构(嵌锁组装、模具热压成形、穿插编织)和金属点阵夹层结构(冲压成形、挤压线切割、拉伸网折叠、搭接拼装、熔模铸造以及增材制造)的主要制造工艺。最后提出如何将设计因子与多目标进行匹配及优化设计,是轻质高强点阵夹层结构的重点研究方向,轻质高强点阵夹层结构将朝多材料及多结构复合方向发展,开发新的制造工艺,提高费效比,是点阵夹层结构材料需解决的问题。     

基于模糊PI控制的瞬态高温控制策略研究

目的通过地面环境试验研究气动热引起的瞬态高温环境对飞行器结构的影响。方法设计基于石英灯和离心机的瞬态高温-加速度复合试验系统,研究温度和加速度同步控制系统的结构和原理,分析无制冷装置环境下瞬态高温控制的难点,提出基于模糊PI控制器的温度控制策略。结果通过MATLAB仿真验证,设计的模糊PI控制器相比传统的PI控制器能够有效提高温度控制的动态性能与精确性。结论将基于模糊PI控制的瞬态加热控制策略应用于瞬态高温控制是可行、有效的,能为地面气动热模拟环境试验提供技术保障。     

芳纶纤维对飞机尾翼结构抗鸟撞性能影响研究

目的研究飞机尾翼结构采用芳纶纤维复合材料的抗鸟撞性能。方法根据芳纶纤维夹芯和芳纶纤维层合板两种飞机尾翼前缘构型,分别建立有限元模型进行仿真计算,分析两种构型鸟撞后的损伤和变形,并对两种构型进行抗鸟撞性能研究试验。结果芳纶夹芯前缘构型前缘凹陷,前梁没有破裂;芳纶层合板前缘构型前缘破裂,前梁有破损。试验结果与仿真分析结果高度吻合。结论芳纶夹芯前缘构型比芳纶层合板前缘构型具有更好的抗鸟撞性能。芳纶纤维层合板构型会造成前缘蒙皮变形过大,前梁腹板破损,导致飞机鸟撞后维修成本较高。     

内饰材料发射率对密封舱室热防护效率的影响

目的探究密封舱室热防护效率与其内饰材料表面发射率的关系,分析内饰材料发射率对其表面温度、舱室内温度的影响规律。方法采用自行设计的小型密封舱室和加热测量装置,对内饰材料表面及舱室内温度进行测量。结果当内饰材料发射率为0.09时,内饰表面温度为141.2℃,舱室内平均温度仅为90.8℃;内饰材料发射率为0.91时,内饰表面温度为124.4℃,舱室内平均温度为109.1℃。结论试样表面温度随材料发射率的提高而降低,舱室内部空气平均温度随材料发射率的提高而升高;试样表面温度与舱室空气平均温度的温度差随材料发射率的提高而减小;同时,相同试样表面温度与舱室平均温度的温度差随加热温度的提高而增加。