Microbial activities in boreal soils: Biodegradation of organic contaminants at low temperature and ammonia oxidation

This thesis deals with the response of biodegradation of selected anthropogenic organic contaminants and natural autochthonous organic matter to low temperature in boreal surface soils. Furthermore, the thesis describes activity, diversity and population size of autotrophic ammonia-oxidizing bacteria (AOB) in a boreal soil used for landfarming of oil-refinery wastes, and presents a new approach, in which the particular AOB were enriched and cultivated in situ from the landfarming soil onto cation exchange membranes. This thesis demonstrates that rhizosphere fraction of natural forest humus soil and agricultural clay loam soil from Helsinki Metropolitan area were capable of degrading of low to moderate concentrations (0.2 50 µg cm-3) of PCP, phenanthrene and 2,4,5-TCP at temperatures realistic to boreal climate (-2.5 to +15 °C). At the low temperatures, the biodegradation of PCP, phenanthrene and 2,4,5-TCP was more effective (Q10-values from 1.6 to 7.6) in the rhizosphere fraction of the forest soil than in the agricultural soil. Q10-values of endogenous soil respiration (carbon dioxide evolution) and selected hydrolytic enzyme activities (acetate-esterase, butyrate-esterase and β-glucosidase) in acid coniferous forest soil were 1.6 to 2.8 at temperatures from -3 to +30 °C. The results indicated that the temperature dependence of decomposition of natural autochthonous soil organic matter in the studied coniferous forest was only moderate. The numbers of AOB in the landfarming (sandy clay loam) soil were determined with quantitative polymerase chain reaction (real-time PCR) and with Most Probable Number (MPN) methods, and potential ammonium oxidation activity was measured with the chlorate inhibition technique. The results indicated presence of large and active AOB populations in the heavily oil-contaminated and urea-fertilised landfarming soil. Assessment of the populations of AOB with denaturing gradient gel electrophoresis (DGGE) profiling and sequence analysis of PCR-amplified 16S rRNA genes showed that Nitrosospira-like AOB in clusters 2 and 3 were predominant in the oily landfarming soil. This observation was supported by fluorescence in situ hybridization (FISH) analysis of the AOB grown on the soil-incubated cation-exchange membranes. The results of this thesis expand the suggested importance of Nitrosospira-like AOB in terrestrial environments to include chronically oil-contaminated soils.

Two-Phase Flow In Fuel Cells In Short-Term Microgravity Condition

A visual observation of liquid-gas two-phase flow in anode channels of a direct methanol proton exchange membrane fuel cells in microgravity has been carried out in a drop tower. The anode flow bed consisted of 2 manifolds and 11 parallel straight channels. The length, width and depth of single channel with rectangular cross section was 48.0 mm, 2.5 mm and 2.0 mm, respectively. The experimental results indicated that the size of bubbles in microgravity condition is bigger than that in normal gravity. The longer the time, the bigger the bubbles. The velocity of bubbles rising is slower than that in normal gravity because buoyancy lift is very weak in microgravity. The flow pattern in anode channels could change from bubbly flow in normal gravity to slug flow in microgravity. The gas slugs blocked supply of reactants from channels to anode catalyst layer through gas diffusion layer. When the weakened mass transfer causes concentration polarization, the output performance of fuel cells declines.

Two-phase Flow in Fuel Cells in Short-term Microgravity Condition

A visual observation of liquid-gas two-phase flow in anode channels of a direct methanol proton exchange membrane fuel cells in microgravity has been carried out in a drop tower. The anode flow bed consisted of 2 manifolds and 11 parallel straight channels. The length, width and depth of single channel with rectangular cross section was 48.0 mm, 2.5 mm and 2.0 mm, respectively. The experimental results indicated that the size of bubbles in microgravity condition is bigger than that in normal gravity. The longer the time, the bigger the bubbles. The velocity of bubbles rising is slower than that in normal gravity because buoyancy lift is very weak in microgravity. The flow pattern in anode channels could change from bubbly flow in normal gravity to slug flow in microgravity. The gas slugs blocked supply of reactants from channels to anode catalyst layer through gas diffusion layer. When the weakened mass transfer causes concentration polarization, the output performance of fuel cells declines.

质子交换膜燃料电池短时微重力性能实验研究

利用落塔开展了不同重力情况下质子交换膜燃料电池性能的实验研究.对常重力和微重力条件下质子交换膜燃料电池发电时其阴极蛇形流场内部的两相流动开展了可视化现场观测.对重力因素对质子交换膜燃料电池内部传质过程的影响进行了分析和讨论.实验结果表明:在常重力环境中,液态水堆积在竖置流道的底部,无法有效排出.聚集在流道内的液态水与反应气体在流道内形成气/液两相流动.在微重力环境中,液态水在气体推动力的作用下从流道的底部上升并沿流道向出口流动.聚集在流道内的液态水排除后,减小了反应气体(氧气)从流道向催化层的传递阻力,从而使质子交换膜燃料电池的性能得到提高.

Catalisadores à base de platina frente a correntes de H2 contendo acetaldeído geradas via reforma do etanol

Devido ao efeito estufa, a produção de hidrogênio a partir da reação de reforma do bioetanol tem se tornado um assunto de grande interesse em catálise heterogênea. Os catalisadores à base de Pt são empregados nos processos de purificação de H2 e também em eletrocatalisadores das células a combustível do tipo membrana polimérica (PEMFC). O hidrogênio obtido a partir da reforma do etanol contém como contaminante o acetaldeído e pequenas quantidades de CO. Assim, pode-se prever que muitas reações podem ocorrer na presença de catalisadores de Pt durante o processo de purificação do H2 e mesmo no próprio eletrocatalisador. Desta forma, este trabalho tem como objetivo descrever o comportamento do acetaldeído na presença de catalisadores de Pt. Para tanto foram preparados dois catalisadores, Pt/SiO2 e Pt/USY, contendo 1,5% de metal em ambos. Também foi estudado um eletrocatalisador (comercial) de Pt suportado em carvão (Pt/C). Os catalisadores foram caracterizados através das técnicas de análise textural, difração de raios X (DRX), quimissorção de H2, reação de desidrogenação do ciclohexano, espectroscopia no infravermelho de piridina adsorvida, dessorção a temperatura programada de n-butilamina (TPD de n-butilamina), dessorção a temperatura programada de CO2 (TPD-CO2), análise termogravimétrica, microscopia eletrônica de varredura (MEV) e espectroscopia de dispersão de energia (EDS). Os testes catalíticos foram realizados entre as temperaturas de 50 e 350 C em corrente contendo acetaldeído, H2 e N2. Foi observado que as propriedades ácido-básicas dos suportes promovem as reações de condensação com formação de éter etílico e acetato de etila. O acetaldeído em catalisadores de Pt sofre quebra das ligações C-C e C=O. A primeira ocorre em uma ampla faixa de temperaturas, enquanto a segunda apenas em temperaturas abaixo de 200 C. A quebra da ligação C-C produz metano e CO. Já a quebra da ligação C=O gera carbono residual nos catalisadores, assim como espécies oxigênio, que por sua vez são capazes de eliminar o CO da superfície dos catalisadores. Nota-se que o tipo de suporte utilizado influencia na distribuição de produtos, principalmente a baixas temperaturas. Além disso, constatou-se que a descarbonilação não é uma reação sensível à estrutura do catalisador. Verificou-se também a presença de resíduos sobre os catalisadores, possivelmente oriundos não somente da quebra da ligação C=O, mas também de reações de polimerização

CO selective oxidation in a microchannel reactor for PEM fuel cell

It is indispensable to remove CO at the level of less than 50ppm in H-2-rich feed gas for the proton exchange membrane (PEM) fuel cells. In this paper, catalyst with high activity and selectivity, and a microchannel reactor for CO preferential oxidation (PROX) have been developed. The results indicated that potassium on supported Rh metal catalysts had a promoting effect in the CO selective catalytic oxidation under H-2-rich stream, and microchannel reactor has an excellent ability to use in on-board hydrogen generation system. CO conversion keeps at high levels even at a very high GHSV as 500 000 h(-1), so, miniaturization of hydrogen generation system can be achieved by using the microchannel reactor. (C) 2004 Elsevier B.V. All rights reserved.

Pt based anode catalysts for direct ethanol fuel cells

In the present work several Pt-based anode catalysts supported on carbon XC-72R were prepared with a novel method and characterized by means of XRD, TEM and XPS analysis. It was found that all these catalysts are consisted of uniform nanosized particles with sharp distribution and Pt lattice parameter decreases with the addition of Ru or Pd and increases with the addition of Sn or W. Cyclic voltammetry (CV) measurements and single direct ethanol fuel cell (DEFC) tests jointly showed that the presence of Sn, Ru and W enhances the activity of Pt towards ethanol electro-oxidation in the following order: Pt1Sn1/C > Pt1Ru1/C > Pt1W1/C > Pt1Pd1/C > Pt/C. Moreover, Pt1Ru1/C further modified by W and Mo showed improved ethanol electro-oxidation activity, but its DEFC performance was found to be inferior to that measured for Pt1Sn1/C. Under this respect, several PtSn/C catalysts with different Pt/Sn atomic ratio were also identically prepared and characterized and their direct ethanol fuel cell performances were evaluated. It was found that the single direct ethanol fuel cell having Pt1Sn1/C or Pt3Sn2/C or Pt2Sn1/C as anode catalyst showed better performances than those with Pt3Sn1/C or Pt4Sn1/C. It was also found that the latter two cells exhibited higher performances than the single cell using Pt1Ru1/C, which is exclusively used in PEMFC as anode catalyst for both methanol electro-oxidation and CO-tolerance. This distinct difference in DEFC performance between the catalysts examined here would be attributed to the so-called bifunctional mechanism and to the electronic interaction between Pt and additives. It is thought that an amount of -OHads, an amount of surface Pt active sites and the conductivity effect of PtSn/C catalysts would determine the activity of PtSn/C with different Pt/Sn ratios. At lower temperature values or at low current density regions where the electro-oxidation of ethanol is considered not so fast and its chemisorption is not the rate-determining step, the Pt3Sn2/C seems to be more suitable for the direct ethanol fuel cell. At 75 degreesC, the single ethanol fuel cell with Pt3Sn2/C as anode catalyst showed a comparable performance to that with Pt2Sn1/C, but at higher temperature of 90 degreesC, the latter presented much better performance. It is thought from a practical point of view that Pt2Sn1/C, supplying sufficient -OHads and having adequate active Pt sites and acceptable ohmic effect, could be the appropriate anode catalyst for DEFC. (C) 2003 Elsevier B.V. All rights reserved.

Influence of catalyst layer structure on the current distribution of PEMFCs

A modified subcell approach was adopted to evaluate the current density distributions of proton exchange membrane fuel cells (PEMFCs) with different electrodes. Conventional hydrophobic electrodes showed better performance under flooding conditions compared to hydrophilic electrodes. The thin-film hydrophilic electrode performed better in the absence of liquid water, but it was more readily flooded. A composite catalyst layer was designed with 2/3 of the area from the inlet prepared hydrophilic and the remaining 1/3 area hydrophobic. The composite catalyst layer with commercial scale dimension showed notable enhanced performance in the concentration polarization region. (C) 2004 The Electrochemical Society.

Studies on state and structure of noble metals in electrocatalyst made by coprecipitation method

The electrocatalysts of Pt/C, PtRu/C and Ru/C were prepared by the impregnation method. The facet characterization, the dispersion and the particle size for the catalysts were determined by means of X-ray diffraction and transmission electron microscopy. X-ray photoelectron spectroscopy was also used to analyze the state and the valency of the noble metals. The results show that the particle size was in nanometer range and the binary metals have come into being an alloy. The platinum in the catalysts existed in zero valency. The valency of the ruthenium on the surface is different from that in the body, while the ruthenium on the surface existed in oxide-form. PtRu/C and Pt/C are of good activity to the electrooxidation of hydrogen except Ru/C. PtRu/C is more tolerant of CO than Pt/C, and CO is only adsorbed on Pt.

An infrared study on Langmuir-Blodgett films of octadecylammonium octadecanoate: FWHM and the vibrational coupling

The monolayer of the mixture of octadecanoic acid and octadecylamine with molar ratio 1: 1 has been investigated at the air-water interface. It was found that the monolayer shows a rather stable state at the surface pressure of 30 mN/m and this monolayer can be transferred onto a CaF2 plate by Langmuir-Blodgett (LB) technique. The infrared spectra of LB films indicated that octadecyl ammonium octadecanoate is formed by an intermolecular proton exchange between adjacent carboxylic and aminic groups (COO- and NH3+). In three-layer LB film, the CH2 scissoring mode of the long hydrocarbon chains of octadecyl ammonium octadecanoate shows a broad band feature at about 1468 cm(-1) while this vibrational mode of three-layer LB film of the mixture (1: 1) of deuterated stearic acid and octadecylamine (octadecylammonium octadecanoate-d35, C18H37NH3+C17D35COO-) only shows a narrow band. The broad feature of the CH2 scissoring mode in octadecylammonium octadecanoate probably originates from the coupling between the chain of stearic acid and that of octadecylamine while this kind of coupling could be completely removed in octadecylammonium octadecanoate-d35.

Electrochemical H2S sensor with H2SO4 pre-treated Nafion membrane as solid polymer electrolyte

It is reported for the first time that the performance of the electrochemical H2S sensor with the Nation membrane pre-treated with the concentrated H2SO4 as the solid electrolyte is much more stable than that for the sensor with the Nation membrane without H2SO4 pretreatment. The sensitivity of the sensor is about 2.92 muA/ppm. The response time of the sensor is about 9 s. The detection limit is about 0.1 ppm. Therefore, this kind of the electrochemical H2S gas sensor may be desirable for the practical application.

Application of modified Nafion membrane to the sulfur dioxide gas electrochemical sensor

The electrochemical SO2 sensor worked at the fixed potential and prepared with Nafion membrane as the solid electrolyte was studied. It v as observed that after Nafion membrane, was treated with H2SO4, the water-preserving ability of the membrane was increased. In turn, the performance of the sensor became stable. After lifetime test for 4 months, the performance of the sensor deceased slightly, Thus this kind of sensor may become a gas sensor for the practical application.

质子交换膜燃料电池在无缆水下机器人上的应用研究

质子交换膜燃料电池(PEMFC)作为一种新兴的能源,在汽车和航天器上已经获得成功的应用,本文针对水下环境和PEMFC的特点,对PEMFC在无缆水下机器人(UUV)上试验应用的关键技术进行讨论.

A comprehensive comparison of fuel options for fuel cell vehicles in China

Fuel cell vehicles (FCVs) offer the potential of ultra-low emissions combined with high efficiency. Proton exchange membrane (PEM) fuel cells being developed for vehicles require hydrogen as a fuel. Due to the various pathways of hydrogen generation, both onboard and off-board, the question about which fuel option is the most competitive for fuel cell vehicles is of great current interest. In this paper, a life-cycle assessment (LCA) model was made to conduct a comprehensive study of the energy, environmental, and economic (3E) impacts of FCVs from well to wheel (WTW). In view of the special energy structure of China and the timeframe, 10 vehicle/fuel systems are chosen as the study projects. The results show that methanol is the most suitable fuel to serve as the ideal hydrogen source for fuel cell vehicles in the timeframe and geographic regions of this study. On the other hand, gasoline and pure hydrogen can also play a role in short-term and regional applications, especially for local demonstrations of FCV fleets. (c) 2004 Elsevier B.V All rights reserved.