Effect of substituents in hydroxyl radical-mediated degradation of azo pyridone dyes: Theoretical approaches on the reaction mechanism

Understanding the degradation behavior of azo dyes in photocatalytic wastewater treatment is of fundamental and practical importance for their application in textile-processing and other coloration industries. In this study, quantum chemistry, as density functional theory, was used to elucidate different degradation pathways of azo pyridone dyes in a hydroxyl radical (HO^?)-initiated photocatalytic system. A series of substituted azo pyridone dyes were synthesized by changing the substituent group in the para position of the benzene moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The effect of dye molecular structure on the photocatalytic degradation reaction mechanism was analyzed and quantification of substituent effects on the thermodynamic and kinetics parameters was performed. Potential energy surface analysis revealed the most susceptible reaction site for the HO^? attack. The calculated reaction barriers are found to be strongly affected by the nature of substituent group with a good correlation using Hammett σ_p constants and experimentally determined reaction rates. The stability of pre-reaction complexes and transition state complexes were analyzed applying the distortion-interaction model. The increased stability of the transition state complexes with the distancing from the substituent group has been established.     

Reactive uptake of NO2 on volcanic particles: A possible source of HONO in the atmosphere

The heterogeneous degradation of nitrogen dioxide (NO₂) on five samples of natural Icelandic volcanic particles has been investigated. Laboratory experiments were carried out under simulated atmospheric conditions using a coated wall flow tube (CWFT). The CWFT reactor was coupled to a blue light nitrogen oxides analyzer (NO_x analyzer), and a long path absorption photometer (LOPAP) to monitor in real time the concentrations of NO₂, NO and HONO, respectively. Under dark and ambient relative humidity conditions, the steady state uptake coefficients of NO₂ varied significantly between the volcanic samples probably due to differences in magma composition and morphological variation related with the density of surface OH groups. The irradiation of the surface with simulated sunlight enhanced the uptake coefficients by a factor of three indicating that photo-induced processes on the surface of the dust occur. Furthermore, the product yields of NO and HONO were determined under both dark and simulated sunlight conditions. The relative humidity was found to influence the distribution of gaseous products, promoting the formation of gaseous HONO. A detailed reaction mechanism is proposed that supports our experimental observations. Regarding the atmospheric implications, our results suggest that the NO₂ degradation on volcanic particles and the corresponding formation of HONO is expected to be significant during volcanic dust storms or after a volcanic eruption.     

京津冀地区钢铁行业协同减排成本-效益分析

京津冀地区是我国钢铁行业布局最集中的区域,也是大气污染治理的重点区域之一.分析京津冀地区钢铁行业各类治污手段中长期减排的成本-效益,对于选择最经济有效的减排路径、加快推动该地区大气环境质量达标意义重大.基于能源环境、环境分布、人群健康效益评价等模块构建多模型耦合方法,以2015年为基准年,以每5 a为时间节点,设计了京津冀地区钢铁行业规模-结构、规模-技术、规模-末端治理、综合减排4种协同减排情景,计算各情景下2015—2030年京津冀地区钢铁行业主要污染物(SO₂、NO_x、PM₁₀、PM_2.5、CO₂)的减排成本与效益,比较获取治污减排的最优路径方案.结果表明:①基于减排成本计算,规模-末端治理减排情景成本最低,分别为规模-结构、规模-技术减排情景投入的15.18%、23.94%;综合减排情景下治污减排潜力最大,但综合成本最高.②基于环境税效益评价方法、人群健康效益评价方法计算显示,人群健康效益评价方法计算的减排效益高于环境税效益评价方法,表明污染减排的潜在人群健康效益更高;基于两种减排效益方法,4种协同减排情景中综合减排效益分别为10.78×108、76.14×108元,高于规模-结构、规模-技术、规模-末端治理减排情景效益.③基于环境税效益评价方法,4种协同减排情景的效益-成本比表现为规模-末端治理减排情景(0.46) >规模-技术减排情景(0.24) >综合减排情景(0.15) >规模-结构减排情景(0.10);基于人群健康效益评价方法4种协同减排情景的效益-成本比依次为规模-末端治理减排情景(8.35) >综合减排情景(1.07) >规模-结构减排情景(0.57) >规模-技术减排情景(0.65),表明规模-末端治理减排情景的减排路径最优.研究显示,京津冀地区钢铁行业应基于环境质量底线目标要求,综合考虑减排潜力、减排成本与收益,以规模-末端治理为主要途径,选取协同减排的最优路径.      

树脂负载Fe3+/Cu2+多相类芬顿降解染料橙黄

制备了新型多相类Fenton催化剂(Fe3+cu2+)/R(Fe3+和cu2+同时负载于离子交换树脂),以橙黄Ⅳ为研究对象,探讨了初始过氧化氢浓度、橙黄Ⅳ浓度、催化剂量、初始pH值及温度等因素对催化反应速率的影响,并对该催化剂重复使用性能进行测试.研究结果表明,该催化剂(Fe3++Cu2+)/R与Fe3+/R相比表现出更好的催化过氧化氢分解的活性,使橙黄Ⅳ的降解率提高10%;催化过氧化氢氧化橙黄Ⅳ的反应遵循假一级反应动力学,反应活化能为10.71 kJ·mol-1;催化剂表现出良好的重复使用性能,Fe3+和cu2+在树脂表面负载比较牢固,具有较好的稳定性和耐用性.同时,电子顺磁共振(EPR)测试结果表明,cu2+的掺杂能有效地促进OH·的产生;X射线光电子能谱(XPS)测试结果表明,反应过程中存在高价态铁物种.因此,在该体系反应过程中产生的活性物种是OH·和高价态铁同时共存.     

Bioaccumulation and depuration of chromium in the selected organs and whole body tissues of freshwater fish Cirrhinus mrigala individually and in binary solutions with nickel

Contamination of aquatic ecosystems with heavy metals has been receiving increased worldwide attention due to their harmful e ects on human health and other organisms in the environment. Most of the studies dealing with toxic e ects of metals deal with single metal species, while the aquatic organisms are typically exposed to mixtures of metals. Hence, in order to provide data supporting the usefulness of freshwater fish as indicators of heavy metal pollution, it has been proposed in the present study to investigate the bioaccumulation and depuration of chromium in the selected organs of freshwater fingerlings Cirrhinus mrigala, individually and in binary solutions with nickel. The results show that the kidney is a target organ for chromium accumulation, which implies that it is also the “critical” organ for toxic symptoms. The results further show that accumulation of nickel in all the tissues of C. mrigala is higher than that of chromium. In addition, the metal accumulations of the binary mixtures of chromium and nickel are substantially higher than those of the individual metals, indicating synergistic interactions between the two metals. Theoretically the simplest explanation for an additive joint action of toxicants in a mixture is that they act in a qualitatively similar way. The observed data suggest that C. mrigala could be suitable monitoring organisms to study the bioavailability of water-bound metals in freshwater habitats.     

Evaluating the e ects of granular and membrane filtrations on chlorine demand in drinking water

In this study, chlorine decay experiments were conducted for the raw water from Nakdong River that is treated by Chilseo Water Treatment Plant (CWTP) situated in Haman, Korea as well as the e uents from sand and granular activated carbon (GAC) filters of CWTP and fitted using a chlorine decay model. The model estimated the fast and slow reacting nitrogenous as well as organic/inorganic compounds that were present in the water. It was found that the chlorine demand due to fast and slow reacting (FRA and SRA) organic/inorganic substances was not reduced significantly by sand as well as GAC filters. However, the treated e uents from those filters contained FRA and SRA that are less reactive and had small reaction rate constants. For the e uents from microfiltration, ultrafiltration, and nanofiltration the chlorine demand because FRA and SRA were further reduced but the reaction rate constants were larger compared to those of sand and GAC filter e uents. This has implications in the formation of disinfection by products (DBPs). If DBPs are assumed to form due to the interactions between chlorine and SRA, then it is possible that the DBP formation potential in the e uents from membrane filtrations could be higher than that in the e uents from granular media filters.     

“绿色革命”能够解决粮食危机吗？

粮食需求不断增加,农业生产却无法跟上它的脚步。2008年出现的粮食价格暴涨,在世界各地都相继引发粮食危机甚至是暴动。在这种背景下,世界是否会出现新一轮农业“绿色革命”呢？     

废啤酒酵母吸附去除水溶液中活性红4

用废啤酒酵母作生物吸附剂吸附水溶液中活性红4(RR4),并对吸附性能进行了评价。通过电位滴定和FTIR分析表明废啤酒酵母上主要存在磺酸基、羧基及氨基等官能团。对溶液pH值、RR4浓度和吸附时间等因素对吸附的影响进行了研究,结果表明:废啤酒酵母对RR4的吸附速率快,320min即可达到吸附平衡;酸性条件利于吸附,碱性条件下则会发生解吸附,pH=11条件下解吸附率高于86%;等温吸附数据符合Langmuir模式,pH=2条件下废啤酒酵母对RR4的最大吸附量为103.36mg/g。     

三峡库区水华优势藻类生长动力学的普适性研究

从蓝绿藻中选取绿藻门的普通小球藻(Chlorella vulgaris,CV藻)为研究对象,应用Monod方程考察氮、磷营养盐对CV藻生长的影响,分别计算出CV藻对TP、TN的半饱和常数KSP和KSN结果表明KSN>>KSP,说明TP对CV藻生长的影响明显大于TN.CV藻生长速率对磷质量浓度反应很灵敏:与空白值相比,在0.002 mg·L-1的低浓度下u就有提高,而浓度到0.2 mg.L-1时,u明显增大;但在0.000-0.050 mg·L-1氮浓度范围内u几乎没有变化.通过系统比较CV藻与优势蓝绿藻,甚至海水藻的生长动力学特征,探讨了CV藻与其它蓝绿藻的动力学普适性和共同性,证实这些藻类都具有非常类似的生长动力学和生态学特征.因此,推测CV藻生长动力学模型可以从整体上反映和代表库区优势蓝绿藻的生长行为.同时分析和归纳了蓝绿藻生长模型的相似性和规律性,得出三峡库区优势藻类生长行为存在普遍一致性的初步结论.