Density functional theory (DFT) studies of vanadium-titanium based selective catalytic reduction (SCR) catalysts

Based on density functional theory (DFT) and basic structure models, the chemical reactions on the surface of vanadium-titanium based selective catalytic reduction (SCR) denitrification catalysts were summarized. Reasonable structural models (non-periodic and periodic structural models) are the basis of density functional calculations. A periodic structure model was more appropriate to represent the catalyst surface, and its theoretical calculation results were more comparable with the experimental results than a non-periodic model. It is generally believed that the SCR mechanism where NH₃ and NO react to produce N₂ and H₂O follows an Eley-Rideal type mechanism. NH₂NO was found to be an important intermediate in the SCR reaction, with multiple production routes. Simultaneously, the effects of H₂O, SO₂ and metal on SCR catalysts were also summarized.     

Mechanism and catalytic performance for direct dimethyl ether synthesis by CO2 hydrogenation over CuZnZr/ferrierite hybrid catalyst

Direct synthesis of dimethyl ether(DME) by CO_2 hydrogenation has been investigated over three hybrid catalysts prepared by different methods:co-precipitation,sol-gel,and solid grinding to produce mixed Cu,ZnO,ZrO_2 catalysts that were physically mixed with a commercial ferrierite(FER) zeolite.The catalysts were characterized by N_2 physisorption,X-ray diffraction(XRD),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),temperature programmed desorption of CO_2(CO_2-TPD),temperature programmed desorption of NH_3(NH_3-TPD),and temperature programmed H2 reduction(H_2-TPR).The results demonstrate that smaller CuO and Cu crystallite sizes resulting in better dispersion of the active phases,higher surface area,and lower reduction temperature are all favorable for catalytic activity.The reaction mechanism has been studied using in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS).Methanol appears to be formed via the bidentate-formate(b-HCOO) species undergoing stepwise hydrogenation,while DME formation occurs from methanol dehydration and reaction of two surface methoxy groups.     

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.     

UV/H2O2 oxidation of tri(2-chloroethyl) phosphate: Intermediate products, degradation pathway and toxicity evaluation

Tri(2-chloroethyl) phosphate (TCEP) with the initial concentration of 5 mg/L was degraded by UV/H₂O₂ oxidation process. The removal rate of TCEP in the UV/H₂O₂ system was 89.1% with the production of Cl^? and PO₄^3? of 0.23 and 0.64 mg/L. The removal rate of total organic carbon of the reaction was 48.8% and the pH reached 3.3 after the reaction. The oxidative degradation process of TCEP in the UV/H₂O₂ system obeyed the first order kinetic reaction with the apparent rate constant of 0.0025 min^?1 (R²=0.9788). The intermediate products were isolated and identified by gas chromatography-mass spectrometer. The addition reaction of HO? and H₂O and the oxidation reaction with H₂O₂ were found during the degradation pathway of 5 mg/L TCEP in the UV/H₂O₂ system. For the first time, environment risk was estimated via the “ecological structure activity relationships” program and acute and chronic toxicity changes of intermediate products were pointed out. The luminescence inhibition rate of photobacterium was used to evaluate the acute toxicity of intermediate products. The results showed that the toxicity of the intermediate products increased with the increase of reaction time, which may be due to the production of chlorine compounds. Some measures should be introduced to the UV/H₂O₂ system to remove the highly toxic Cl-containing compounds, such as a nanofiltration or reverse osmosis unit.     

底泥原位洗脱过程中氮磷含量与形态变化特征

随着城市化进程的不断推进,城市河流底泥中内源氮磷污染问题日益突出.为研究原位洗脱技术对污染底泥中氮、磷物质和成分的作用效果,以北京市凉水河作为研究对象,分别比较了现场试验洗脱与对照组0~30 cm分层底泥以及实验室模拟洗脱处理前后0~10 cm底泥中pH、E_h（氧化还原电位）、容重、含水率、OM（有机质）、TN、TP和氮、磷形态分布的变化特征.结果表明:①现场洗脱对0~5 cm厚度底泥的处理和模拟洗脱处理均对底泥中pH、E_h、含水率的改变以及其中TN、TP的去除效果表现显著,其中,现场试验洗脱组0~5 cm范围底泥中w（TN）、w（TP）分别较对照组降低了66.4%±17.4%、40.8%±24.4%,模拟洗脱处理对底泥中OM、TN、TP的去除率分别达70.1%±4.8%、66.8%±2.0%、43.1%±3.1%.②原位洗脱技术对底泥中TN的去除主要通过对PON（颗粒态有机氮）的去除来实现,现场和模拟试验过程中PON对TN去除的贡献率分别达55.0%和73.6%.③原位洗脱对底泥中TP的去除主要通过对Al-P（铝结合态磷）、OP（有机磷）的去除来实现,现场和模拟试验中Al-P、OP对TP去除的贡献率分别达37.0%、66.2%和31.3%、43.7%.研究显示,原位洗脱技术可有效去除城市河流底泥处理层中的氮磷物质,并以有机氮、磷物质的去除为主.      

不同浓度锌处理下水稻幼苗对镉的累积效应

为探究锌（Zn）对水稻镉（Cd）累积的影响及其根表铁膜所发挥的作用,选取Cd高累积型水稻品种中9优547（简称"Z547"）和Cd低累积型水稻品种金优402（简称"J402"）,采用温室水培试验,研究0、2、5、10、15和20 μmol/L等6个Zn浓度下水稻幼苗对Cd的累积效应,以及不同浓度Zn处理对根表铁膜生成量的影响.结果表明:①随着c（Zn）的增加,Z547和J402水稻幼苗生物量均呈先增后减的趋势,分别在c（Zn）为2和10 μmol/L时达到最大值.②Z547和J402水稻幼苗中w（Cd）均呈先降后增的趋势,分别在c（Zn）为5和2 μmol/L时达到最小值;当水稻幼苗中w（Cd）达到最小值时,Z547根和地上部中w（Cd）分别为31.65和11.47 mg/kg,J402根和地上部中w（Cd）分别为22.58和14.36 mg/kg.③不同浓度Zn处理下水稻幼苗各部位中w（Cd）均与根表铁膜中w（Mn）、w（Fe）、w（Fe+Mn）呈显著正相关,高铁膜处理水稻幼苗中w（Cd）显著高于低铁膜处理,表明根表铁膜生成量的增加会促进Cd在水稻幼苗中的累积.研究显示,当c（Zn）较低时,c（Zn）的增加会抑制水稻幼苗对Cd的累积;当c（Zn）较高时,c（Zn）的增加会促进水稻幼苗对Cd的累积,而Zn可通过控制根表铁膜的生成来影响水稻幼苗对Cd的累积.      

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.      

On-going nitrification in chloraminated drinking water distribution system (DWDS) is conditioned by hydraulics and disinfection strategies

Within the drinking water distribution system (DWDS) using chloramine as disinfectant, nitrification caused by nitrifying bacteria is increasingly becoming a concern as it poses a great challenge for maintaining water quality. To investigate efficient control strategies, operational conditions including hydraulic regimes and disinfectant scenarios were controlled within a flow cell experimental facility. Two test phases were conducted to investigate the effects on the extent of nitrification of three flow rates (Q = 2, 6, and 10 L/min) and four disinfection scenarios (total Cl₂=1 mg/L, Cl₂/NH₃-N=3:1; total Cl₂=1 mg/L, Cl₂/NH₃-N=5:1; total Cl₂=5 mg/L, Cl₂/NH₃-N=3:1; and total Cl₂=5 mg/L, Cl₂/NH₃-N=5:1). Physico-chemical parameters and nitrification indicators were monitored during the tests. The characteristics of biofilm extracellular polymetric substance (EPS) were evaluated after the experiment. The main results from the study indicate that nitrification is affected by hydraulic conditions and the process tends to be severe when the fluid flow transforms from laminar to turbulent (2300<Re<4000). Increasing disinfectant concentration and optimizing Cl₂/NH₃-N mass ratio were found to inhibit nitrification to some extend when the system was running at turbulent condition (Q = 10 L/min, Re = 5535). EPS extracted from biofilm that was established at the flow rate of 6 L/min had greater carbohydrate/protein ratio. Furthermore, several nitrification indicators were evaluated for their prediction efficiency and the results suggest that the change of nitrite, together with total organic carbon (TOC) and turbidity can indicate nitrification potential efficiently.     

Chemical characteristics of road dust PM2.5 fraction in oasis cities at the margin of Tarim Basin

In order to understand the compositions characteristics of particulate matter with aerodynamic diameter less than 2.5 μm (PM_2.5) fraction in road dust (RD_2.5) of oasis cities on the edge of Tarim Basin, 30 road dust (RD) samples were collected in Kashi, Cele, and Yutian in the spring, 2018, and RD_2.5 was collected using the resuspension approach. Eight water-soluble ions, 39 trace elements and 8 fractions of carbon-containing species in PM_2.5 were analyzed. Ca²⁺ and Ca were the most abundant ions and elements in RD_2.5 (7.1% and 9.5%). Cl^- in RD_2.5 was affected not only by attributed to saline-alkali soils in oasis cities of the Tarim Basin and dust from Taklimakan Desert but also by human activities. Moreover, the organic carbon/elemental carbon (OC/EC) ratio indicated that carbon components in RD_2.5 in Cele town mainly come from fossil fuel combustion, while those in Yutian and Kashi mainly come from biomass combustion. It is noteworthy that high Ca in RD_2.5 was seriously affected by anthropogenic emissions, and high Na and K contents in RD_2.5 could be derived from soil and desert dust. It was estimated that Cd, Tl, Sn and Cr were emitted from anthropogenic emissions using the enrichment factor. The coefficients of divergence (COD) result indicated that the influence of local emission on road dust emission is greater than that of long-distance transmission. This study is the first time to comprehensively analyze the chemical characteristics of road dust in oasis cities, and the results provides the sources of road dust at the margin of Tarim Basin.