Improved vacuum-UV (VUV)-initiated photomineralization of organic compounds in water with a xenon excimer flow-through photoreactor (Xe2* lamp, 172 nm) containing an axially centered ceramic oxygenator

Xenon excimer (Xe2*) lamps can be used for the oxidation and mineralization of organic compounds in aqueous solution. This vacuum-ultraviolet (VUV) photochemical method is mainly based on the photochemically initiated homolysis of water that produces hydrogen atoms and hydroxyl radicals. The efficiency of substrate oxidation and mineralization is limited markedly due to the high absorbance of water at the emission maximum of the Xe2* lamp (lambda(max)=172 nm). This photochemical condition generates an extreme heterogeneity between the irradiated volume V(irr) and the non-irradiated ("dark") bulk solution. During VUV-initiated photomineralization of organic substrates, the fast scavenging of hydrogen atoms and of carbon-centered radicals by dissolved molecular oxygen produces a permanent oxygen deficit within V(irr) and adjacent compartments. Hence, at a constant photon flux the concentration of dissolved molecular oxygen within the zones of photo and thermal radical reactions limits the rate of mineralization, i.e. the rate of TOC diminution. Thus, a simple and convenient technique is presented that overcomes this limitation by injection of molecular oxygen (or air) into the irradiated volume by use of a ceramic oxygenator (aerator). The tube oxygenator was centered axially within the xenon excimer flow-through lamp. Consequently, the oxygen or air bubbles enhanced the transfer of dissolved molecular oxygen into the VUV-irradiated volume leading to an increased rate of mineralization of organic model compounds, e.g. 1-heptanol, benzoic acid and potassium hydrogen phthalate.     

Postgraduale Weiterbildung, Nachwuchsf?rderpreis 2005, Jahrestagung 2006 in Landau

Ohne Zusammenfassung     

Chemisch-analytische Untersuchung von Arsenkampfstoffen und ihren Metaboliten

Zusammenfassung  Arsenkampfstoffe sind in der Umwelt persistent und kontaminieren bis heute Boden und Grundwasser. In diesem Beitrag werden die chemischen Reaktionen der Arsenkamptstoffe Diphenylarsinchlorid (CLARK I), Phenylarsindichlorid (PFIFFIKUS), Ethylarsindichlorid (DICK) sowie von Chlorvinylarsinverbindungen (LEWISITE) dargestellt. Die M?glichkeiten der chemisch-analytischen Erfassung dieser chemischen Kampfstoffe als Originalsubstanzen und als Thiol-Derivate werden pr?sentiert.      

Effects of ethanol addition on micellar solubilization and plume migration during surfactant enhanced recovery of tetrachloroethene

Alcohol addition has been suggested for use in combination with surfactant flushing to enhance solubilization kinetics and permit density control of dense non-aqueous phase liquid (DNAPL)-laden surfactant plumes. This study examined the effects of adding ethanol (EtOH) to a 4% Tween 80 (polyoxyethylene (20) sorbitan monooleate) solution used to flush tetrachloroethene (PCE)-contaminated porous media. The influence of EtOH concentration, subsurface layering and scale on flushing solution delivery and PCE recovery was investigated through a combination of experimental and mathematical modeling studies. Results of batch experiments demonstrated that the addition of 2.5%, 5% and 10% (wt.) EtOH incrementally increased the PCE solubilization capacity and viscosity of the surfactant solution, while reducing solution density from 1.002 to 0.986 g/cm3. Effluent concentration data obtained from one-dimensional (1-D) column experiments were used to characterize rate-limited micellar solubilization of residual PCE, which was strongly dependent upon flow velocity and weakly dependent upon EtOH concentration. Two-dimensional (2-D) box studies illustrated that minor differences (0.008 g/cm3) between flushing and resident solution density can strongly influence surfactant front propagation. A two-dimensional multiphase simulator, MISER, was used to model the influence of EtOH composition on the aqueous flow field and PCE mass recovery. The ability of the numerical simulator to predict effluent concentrations and front propagation was demonstrated for both 1-D columns and 2-D boxes flushed with EtOH-amended Tween 80 solutions. Results of this study quantify the potential influence of alcohol addition on surfactant solution properties and solubilization capacity, and demonstrate the importance of considering small density variations in remedial design.     

Photodynamic action of some sensitizers by photooxidation of luminol

We report the development of a novel simple experimental method which allows the comparison of new photosensitizers based on their production of reactive oxygen species. A high-performance liquid chromatography (HPLC) assay permits the monitoring of several substances (sensitizer, reactant and oxidized end product) simultaneously on a single chromatogram. Photoreactions were monitored throughout their course by the HPLC assay surveying the sensitizers' efficiency of singlet oxygen production by the oxidative decomposition of luminol. Several photosensitizers were tested: Rose Bengal, Methylene Blue, Protoporphyrin IX, Photosan III, Photofrin, Hypericin and Pseudohypericin. Additionally, photoreactions were monitored by a standard pO₂ detection system. The measurements of the two detection methods were strongly correlated. Rose Bengal proved to be the most efficient photosensitizer, clearly decreasing the luminol concentration and causing a corresponding increase in aminophthalic acid. Our experiments show that when factors necessary for photochemical reactions are absent or are blocked (antioxidants), no reaction can be detected.     

罗斯比中心区域气候模型Ⅱ:北极圈气候的应用

作为ARCMIP国际计划的一部分,罗斯比中心区域气候模型(RCA2)针对整个北冰洋地区的气候作了数值模拟整合,并与来自sHEBA数据集的观测资料作了比较,RCA2标准模型对北极冬季的云量和长波辐射的模拟较实况偏多.通过引入新的云量参数化方案(该参数化方案显著地改进了云量的年循环)减少了这部分误差,确定了介于晴空向下大气长波辐射与云层底部的长波辐射的补偿率,利用可以更准确描述冰晶与太阳辐射相互作用的辐射方案修正了模型,从而使得模型对云-太阳辐射间的相互作用的描述更接近实际.在模拟晴空辐射部分,由于太阳辐射大气透射率过大,经常在边界层云的顶部产生正偏差.引入真实海冰和积雪两种表面反照率的时间变化,对准确模拟地面能量净收支是至关重要的.同样,为了准确模拟北极圈地区近地面的热力学过程,将雪面温度作为预报量引入模型中也似乎是必不可少的.