绿色工艺无溶剂合成β-羰基膦酸酯（英文）

β-羰基膦酸酯具有广泛的生物学活性,在著名的Horner-Wadsworth-Emmons(HWE)反应中用于合成α,β-不饱和羰基化合物.为克服现有合成β-羰基膦酸酯类化合物的方法存在的缺陷,在一种无溶剂环境下利用烯烃、亚磷酸酯和氧气为原料,铜/铁共催化氧膦化酯制备β-羰基膦酸酯.结果显示:该反应具有良好的选择性和底物普适性,利用简单易得的起始物料有效地获得一系列β-羰基膦酸酯,并能获得32%-77%的收率.此外,将该反应放大至10克级其收率没有显著下降.进一步利用1H NMR、13C NMR、31P NMR及HRMS等技术对β-羰基膦酸酯化合物进行了结构表征.本研究提供了一种实用、成本低廉、高效、绿色工艺合成β-羰基膦酸酯的方法.     

可渗透反应墙在土壤和地下水修复中的应用

近年来,一种新型土壤修复技术逐渐在国外发展并开始商业应用。可渗透反应墙技术(Permeable reactive barrier)具有可渗透性和可原位修复的特点,解决了扰动地下水流动和大量因异位搬迁造成的工程成本高的问题。本文总结了国内外可渗透反应墙应用的几种主要技术,介绍了可渗透反应墙的基本概念、组成、参数的选取、常用的可渗透反应墙的类型和几种新型的可渗透反应墙,并提出一些新的展望。     

合成的黄铁矿还原固定地下水中铼的初步探究

为研究黄铁矿对放射性核素锝的去除效果,实验室采用元素铼(Re)代替锝(Tc),利用氯化铁(FeCl3)与硫氢化钠(NaHS)反应人工合成黄铁矿(FeS2),并将其应用于还原固定高铼酸根(ReO4-)。实验在不同pH值、有机碳含量条件下进行,对FeS2还原固定高铼酸根的动力学性质进行研究与分析,为硫铁矿处理锝提供了必要的依据。FeS2与高铼酸根的还原反应符合准一级反应,在偏酸性、未加入有机碳的情况下,FeS2还原铼的处理效果较好。     

大山包黑颈鹤对旅游干扰的行为反应研究

利用警戒距离和惊飞距离两个指标来反映黑颈鹤对旅游干扰的耐受性。实验表明人数的不同对黑颈鹤的惊飞距离有所不同。研究还表明游客的干扰类型以喧哗为主,占总数的73.10%。噪音分贝对黑颈鹤的警戒距离有极显著影响(p=0.0000.05)。为了在提高游客旅游体验的同时,消除旅游活动对黑颈鹤的不利影响,建议最小接近区域面积=π×39.112=4802.92m2,该区域范围内限制游客进入,并在外围设立障碍物。     

不同氧化锰矿物与砷的交互作用

利用从土壤铁锰结核中分离筛选得到的1株锰氧化细菌(芽孢杆菌,Bacillus sp.)GY16合成生物氧化锰,与化学合成的水钠锰矿进行比较,研究了不同氧化锰对As的氧化吸附特征.结果表明,生物氧化锰和化学氧化锰对As(Ⅲ)均有强烈的氧化作用,化学氧化锰对As(Ⅲ)的氧化速率要高于生物氧化锰,而单位物质的量的生物氧化锰对As(Ⅲ)的氧化量可达化学氧化锰的5倍,并且对As(Ⅴ)有非常明显的吸附作用,而化学氧化锰对As(Ⅴ)的吸附量则非常少.此外,随着生物氧化锰与As(Ⅲ)/As(Ⅴ)反应的进行,生物氧化锰对As(Ⅲ)/As(Ⅴ)的氧化吸附速率均逐渐降低.随着pH的增加,生物氧化锰对As(Ⅲ)的氧化量及As(Ⅴ)的吸附量均呈现出明显的下降趋势,但是化学氧化锰对As(Ⅴ)的吸附量却有微弱的增加.研究结果可为生物氧化锰应用于环境修复提供可靠的技术支撑.     

间歇式生物反应器中PHACs的吸附降解性及动力学特性

利用间歇反应器考察了非那西丁(PNT)、吉非罗齐(GFZ)、咖啡因(CAF)、双氯芬酸(DCF)和胆固醇(CH)5种医药类污染物分别在厌氧、缺氧及好氧条件下的吸附与降解特性,并通过动力学拟合深入考察目标物的降解速率及所符合的反应级数.研究表明,PNT在4 h内就能得到100%的降解,GFZ与CH能通过吸附与降解得到部分或全部去除.好氧条件下目标物的泥水分配系数kp值与降解速率均高于缺氧与厌氧条件,好氧条件下CAF的去除率达到99%以上.5种目标物除PNT外都有不同程度的吸附,目标物的污泥吸附能力为CHDCFGFZCAF;动力学拟合结果表明,生物降解动力学一级反应速率PNTCAF,二级反应速率CHGFZ;DCF几乎不能被生物降解,但符合二级吸附动力学模型,其平衡吸附量最高可达总投加量的71%.     

Heterogeneous Fenton-like degradation of 4-chlorophenol using iron/ordered mesoporous carbon catalyst

Ordered mesoporous carbon supported iron catalysts(Fe/OMC) were prepared by the incipient wetness impregnation method and investigated in Fenton-like degradation of 4-chlorophenol(4CP) in this work. XRD and TEM characterization showed that the iron oxides were well dispersed on the OMC support and grew bigger with the increasing calcination temperature. The catalyst prepared with a lower calcination temperature showed higher decomposition efficiency towards 4CP and H2O2, but more metals were leached. The effect of different operational parameters such as initial pH, H2O2 dosage, and reaction temperature on the catalytic activity was evaluated. The results showed that 96.1% of 4CP and 47.4% of TOC was removed after 270 min at 30°C, initial pH of 3 and 6.6 mmol/L H2O2. 88% of 4CP removal efficiency was retained after three successive runs, indicating Fe/OMC a stable catalyst for Fenton reaction. 4CP was degraded predominately by the attack of hydroxyl radical formed on the catalyst surface and in the bulk solution due to iron leaching. Based on the degradation intermediates detected by high performance liquid chromatography, possible oxidation pathways were proposed during the 4CP degradation.     

Photocatalytic removal of NO and NO2 using titania nanotubes synthesized by hydrothermal method

In this study, the photocatalysts of titania nanotubes(TNTs) were synthesized at different calcination temperatures using commercial Degussa TiO2(P25) as a precursor. The materials were then characterized by BET, SEM, TEM, and XRD analyses. The photocatalytic reactions with NO and NO2 under UV-A irradiation were both performed. The results showed that the photocatalytic reaction rate of NO was much faster than that of NO2, and the conversion of NO2 to nitrate was the rate-limiting step for photocatalytic removal of NOx if the nitrate produced cannot be removed continuously from the photocatalyst surface. For TNTs calcined at different temperatures, a significant enhancement was observed on the total NOx removal efficiency by TNT calcined at 500°C for both NO and NO2 photocatalytic reaction, which could be attributed to its high anatase crystallinity as well as high surface area. These two factors affect primarily on the NO2conversion step in which the high anatase crystallinity could be responsible for the high efficiency at the beginning, while the high surface area could be accounted for retaining this high efficiency from nitric acid poisoning during the test period.     

Combination of heterogeneous Fenton-like reaction and photocatalysis using Co-TiO2 nanocatalyst for activation of KHSO5 with visible light irradiation at ambient conditions

A novel coupled system using Co–Ti O2 was successfully designed which combined two different heterogeneous advanced oxidation processes, sulfate radical based Fenton-like reaction（SR-Fenton） and visible light photocatalysis（Vis-Photo）, for degradation of organic contaminants. The synergistic effect of SR-Fenton and Vis-Photo was observed through comparative tests of 50 mg/L Rhodamine B（Rh B） degradation and TOC removal. The Rhodamine B degradation rate and TOC removal were 100% and 68.1% using the SR-Fenton/Vis-Photo combined process under ambient conditions, respectively. Moreover, based on XRD, XPS and UV-DRS characterization, it can be deduced that tricobalt tetroxide located on the surface of the catalyst is the SR-Fenton active site, and cobalt ion implanted in the Ti O2 lattice is the reason for the visible light photocatalytic activity of Co–Ti O2. Finally, the effects of the calcination temperature and cobalt concentration on the synergistic performance were also investigated and a possible mechanism for the synergistic system was proposed. This coupled system exhibited excellent catalytic stability and reusability,and almost no dissolution of Co2＋was found.     

Multiple biomarkers response in maize (Zea mays L.) during exposure to copper

Biomarkers in higher plants played an important role to estimate exposure effects of pollutants in soil ecosystem and have received increasing attention in recent years. The qualitative and quantitative modifications arising in amplified fragment length polymorphism （AFLP） profiles as a measure of DNA effects were compared with a number of parameters, namely, the root length, total soluble protein content in root tips, chlorophylls content and shoot size to select the most sensitive biomarker responding to copper stress in the range of 0--600 mg/kg. The changes occurring in AFLP profiles of root tips following Cu treatment included loss of normal bands and appearance of new bands and variation in band intensity in comparison to that of the normal seedlings, A reduction in root length was observed at the 200 mg/kg of copper, which was accompanied with a decrease in total soluble protein content. According to their sensitivity to the copper toxicity, the above indicator rank in the following order： AFLP profiles 〉 total soluble protein content 〉 root length 〉 chlorophylls content 〉 shoot. We concluded that the AFLP offered a useful alternative hiomarker assay for the detection of genotoxic effects of environmental pollutants.