Electrochemical oxidation of herbicide bifenox acid in aqueous medium using diamond thin film electrode

The electrochemical oxidation of bifenox acid was studied at a boron-doped diamond thin film by cyclic voltammetry and galvanostatic electrolysis. The course of the electrolysis was monitored by measurement of chemical oxygen demand (COD) and by gas chromatography/mass spectrometry (GC / MS) analysis. It was found that exhaustive electrolysis leads to degradation and, ultimately, to mineralization of the starting herbicide. The degradation intermediates were identified showing that the oxidation process begins with the fragmentation of the molecule followed by reactions involving the hydroxyl radical, which is generated by the discharge of water. The study of the effect of current density and concentration showed that the degradation efficiency increases with decreasing current densities and increasing concentrations. The whole results were interpreted in a mechanistic scheme involving two oxidation pathways, the first is a direct oxidation at the electrode and the second uses hydroxyl radical as mediator of the oxidation. Finally, a kinetic study based on spectrophotometric measurements showed that the degradation process is pseudo first order.     

Will photosynthetic capacity of aspen trees acclimate after long-term exposure to elevated CO2 and O3?

Photosynthetic acclimation under elevated carbon dioxide (CO₂) and/or ozone (O₃) has been the topic of discussion in many papers recently. We examined whether or not aspen plants grown under elevated CO₂ and/or O₃ will acclimate after 11 years of exposure at the Aspen Face site in Rhinelander, WI, USA. We studied diurnal patterns of instantaneous photosynthetic measurements as well as A/C_i measurements monthly during the 2004-2008 growing seasons. Our results suggest that the responses of two aspen clones differing in O₃ sensitivity showed no evidence of photosynthetic and stomatal acclimation under either elevated CO₂, O₃ or CO₂ + O₃. Both clones 42E and 271 did not show photosynthetic nor stomatal acclimation under elevated CO₂ and O₃ after a decade of exposure. We found that the degree of increase or decrease in the photosynthesis and stomatal conductance varied significantly from day to day and from one season to another.     

水体中常见无机阳离子对TiO2薄膜光催化还原Cr（Ⅵ）的影响

选择了6种水体中常见的阳离子（Na^＋、Mg^2＋、Ca^2＋、Al^3＋、Cu^2＋、Ni^2＋）,分别考查了其对TiO2薄膜光催化还原Cr（Ⅵ）的影响;从光吸收、无机离子本身的性质对光生电子的捕获及传递等讨论了上述离子影响TiO2薄膜光催化还原Cr（Ⅵ）的反应速率的原因。结果表明：由于其不能捕获光生电子,Na^＋、Mg^2＋、Ca^2＋本身对TiO2薄膜光催化还原Cr（Ⅵ）的反应速率影响不大;Al^3＋吸引电子能力较强,成为光生电子和Cr（Ⅵ）之间的桥梁,促进了Cr（Ⅵ）的还原;浓度为1 mmmol/L时,Cu^2＋显著地促进了Cr（Ⅵ）的光催化还原,其主要原因是Cu^2＋捕获光生电子的能力很强,起到了催化剂的作用,而浓度大于10 mmol/L时,Cu^2＋形成单质Cu以及对紫外光的吸收都使促进作用降低;Ni^2＋未充满的d轨道具有获得并传递光生电子的能力,也促进了Cr（Ⅵ）的还原;在浓度同为1mmol/L时,对Cr（Ⅵ）光催化还原的促进作用依次为：Cu^2＋〉Al^3＋〉Ni^2＋〉Na^＋、Ca^2＋、Mg^2＋。     

Factors influencing on the bioaccessibility of polybrominated diphenyl ethers in size-specific dust from air conditioner filters

Size-specific concentrations and bioaccessibility of polybrominated diphenyl ethers (PBDEs) in dust from air conditioner filters were measured, and the factors influencing the PBDE bioaccessibility were determined. Generally, the PBDE concentrations increased with decreasing dust particle size, and BDE209 (deca-BDE) was generally the predominant congener. The bioaccessibility ranged from 20.3% to 50.8% for tri- to hepta-BDEs, and from 5.1% to 13.9% for BDE209 in dust fractions of varied particle size. The bioaccessibility of most PBDE congeners decreased with increasing dust particle size. The way of being of PBDE (adsorbed to dust surface or incorporated into polymers) in dust significantly influenced the bioaccessibility. There was a significant negative correlation between the tri- to hepta-BDE bioaccessibility and organic matter (OM) contents in dust. Furthermore, tri- to hepta-BDE bioaccessibility increased with increasing polarity of OMs, while with decreasing aromaticity of OMs. The tri- to hepta-BDE bioaccessibility significantly positively correlated with the surface areas and pore volumes of dust. Using multiple linear regression analysis, it was found that the OM contents and pore volumes of dust were the most important factors to influence the tri- to hepta-BDE bioaccessibility and they could be used to estimate the bioaccessibility of tri- to hepta-BDEs according to the following equation: bioaccessibility (%) = 45.05 − 0.49 × OM% + 1.79 × pore volume. However, BDE209 bioaccessibility did not correlate to any of these factors.     

The Characterisation of Settled Dust by Scanning Electron Microscopy and Energy Dispersive X-ray Analysis

Settled dust has been collected inside the main foyers ofthree University buildings in Wolverhampton City Centre,U.K. Two of the three buildings are located in a streetcanyon used almost exclusively by heavy duty dieselvehicles. The dust was collected on adhesive carbonspectro-tabs to be in a form suitable for analysis byscanning electron microscope and energy dispersive X-rayanalysis. Using these analytical techniques, individualparticle analysis was undertaken for morphology andchemistry. Seasonal variations and variations due tolocation were observed in both the morphologicalmeasurements and chemical analysis. Many of the differencesappear attributable to the influence of road traffic, inparticular, the heavy duty diesel vehicles, travellingalong the street canyon.     

土壤及铁锰结核中锰氧化菌的氧化特性分析

利用从土壤铁锰结核及其附近土壤中分离筛选得到的4株锰氧化菌,研究了不同pH、Mn(Ⅱ)初始浓度下菌株的锰氧化效率及生长情况,并用SEM-EDS及TEM对菌株WHS26、GY16形成的生物氧化锰及水羟锰矿进行了表征.结果表明,pH及Mn(Ⅱ)初始浓度对菌株的锰氧化效率均有影响,4株菌在pH 7~8、Mn(Ⅱ)初始浓度为10~20 mmol·L-1时,锰氧化效率最高;GY16、WHS26形成的生物氧化锰的形貌与化学合成的水羟锰矿存在明显差异,前者呈胶膜状附着在菌株表面,后者呈结晶态.该结果可为生物氧化锰应用于重金属污染修复提供技术支撑.     

Ce-MCM-22分子筛的合成与吸附动力学研究

采用静态水热晶化法,以硅溶胶为硅源、六亚甲基亚胺(HMI)为模板剂,通过掺杂Ce合成了具有MWW层状结构的Ce-MCM-22分子筛。并利用粉末X-射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)等方法对其进行了表征,对其进行了吸附动力学的研究。研究表明,Ce-MCM-22吸附动力方程拟一级方程为y=-0.028 1x-0.136,R2=0.983 4。Ce-MCM-22吸附动力方程拟二级方程为y=0.465 7x+1.2005,R2=0.999 5,说明拟二级反应模型更能真实地反映分子筛吸附亚甲蓝溶液的反应机理。     

厌氧氨氧化电子受体的研究

在无机条件下,以该课题组已经培养出来的厌氧氨氧化污泥作为接种污泥,分别以硫酸盐、硝酸盐和亚硝酸盐为电子受体来研究氨的氧化反应。从去除速率的角度来看,以NO2--N、NO3--N和SO42--S为电子受体的反应器,分别在运行的第24.5天、40天和31天时达到0.030 0 kg/(m.3d)NH4+-N去除速率,则氧化氨的能力由大到小依次是:亚硝酸盐>硫酸盐>硝酸盐;从标准吉布斯自由能变化来看,3种反应都是可以发生的;以亚硝酸盐为电子受体的反应过程是一个消耗酸度的生物过程,而以硫酸盐为电子受体的反应过程是一个消耗碱度的生物过程。     

不同能量电子辐照下星用瑞侃导线性能退化研究

目的研究卫星上外露导线在空间辐射环境下的耐受能力。方法通过分析GEO轨道下在轨10年航天器外露瑞侃导线的辐照环境,研究低能和高能电子对导线性能的影响,地面模拟试验参数选择能量分别为45 keV和1 MeV,注量率均为8.3×10^10 e/(cm^2·s),总注量均为2×10^16 e/cm^2。考察瑞侃导线力学性能(断裂伸长率、拉伸强度)和电性能(击穿电压)的退化情况,并用XPS和SEM测试分析手段,对其电子辐照损伤机理进行研究。结果在不同能量电子辐照下,瑞侃导线的力学性能均略有下降,没有显著区别,而电学性能严重退化,且低能电子较高能电子对其电学性能影响更为严重,其击穿电压分别下降了100%和50%。结论通过剂量-深度分布计算,45 keV入射电子能量全部沉积在样品表层下数微米的深度范围内,完全被导线外皮吸收,对样品的损伤较大;而1 MeV入射电子能量绝大部分穿透表皮沉积在样品铜芯中,因而其性能退化情况相对低能电子较小。进一步的,通过SEM和XPS测试和分析发现,电子辐照造成瑞侃导线分子链降解,形成自由基以及气体,自由基的再交联是造成瑞侃导线损伤的重要机理。     

不同制备温度的水稻生物炭电子交换能力研究

为探究不同热解温度下生物炭的电子交换能力,通过限氧升温炭化法,利用水稻秸秆在不同热解温度条件下制备生物炭,与氧气、铁氰化钾氧化剂和柠檬酸钛还原剂进行氧化还原反应,对生物炭的得电子能力（EAC）和失电子能力（EDC）进行定量分析.结果显示,热解温度对生物炭的电子交换能力有较大影响,随热解温度升高至500℃时,生物炭的EAC和EDC达到最大,分别为3.86,1.72mmol/g高于500℃后,随着温度的增加,EAC和EDC逐渐减小,这是由于生物炭的醌类和酚类官能团的结构改变以及持久性自由基强度变化的联合作用.此外,柠檬酸钛和连二硫酸钠两种氧化还原电位不同的还原剂进一步证实了还原剂电位对生物炭EAC的影响.且生物炭具有氧化还原的可逆性,可逆的EAC与EDC之和近似等于生物炭的电子储存能力.