Determination of the standard heterogeneous rate constant in polyelectrolyte using steady state microdisk voltammograms

The steady state voltammogram at a microdisk electrode is used to measure the diffusion coefficient and standard heterogeneous rate constant (k(s)) of ferrocene in polyelectrolyte PEG + LiClO4. The k(s) obtained is smaller in polyelectrolyte than in liquid medium. It is proposed that the polymer solvent electron transfer dynamics are affected by the relaxation rates of the ether dipole sites on the polymer chains, which are in turn constrained by the rates of polymer chain segment, or local structure, relaxations. The dependence of k(s) on temperature is observed. The k(s) increases with increasing temperature.

STUDY ON ELECTROCATALYTIC OXIDATION OF NADH BY FERROCENE DERIVATIVES AND DETERMINATION OF CATALYTIC RATE-CONSTANT AT MICRODISK ELECTRODE

The electrocatalytic oxidation of NADH by ferrocene derivatives and the influence of complexation with beta-cyclodextrin (beta-CD) were investigated at a microdisk electrode in a buffer solution. The cyclic voltammetric behavior of the ferrocene derivatives on the microdisk electrode was used to determine the electron-transfer rate constant from NADH to the ferricinium species. The heterogeneous rate constants and the diffusion coefficient of ferrocene derivatives were determined with the microdisk electrode. The effect of temperature and pH on the electrocatalytic oxidation of NADH were assessed.

APPLICATIONS OF RAPID SCAN SPECTROELECTROCHEMISTRY - DETERMINATION OF HETEROGENEOUS ELECTRON-TRANSFER RATE-CONSTANT OF BILIVERDIN OXIDATION

The rapid scan spectrometer was used to determine the heterogeneous electron transfer rate parameters for the oxidation of Biliverdin in DMF by single potential step thin layer spectroelectrochemical techniques and yielded an average formal heterogeneous electron transfer rate constant K(s, h)0' = 2.45 (+/-0.12) x 10(-4) cm s-1, electrochemical transfer coefficient alpha = 0.694+/-0.008. The oxidation process of Biliverdin was also studied and the formal potential E0 = 0.637 V (vs. Ag/AgCl) was obtained.

DETERMINATION OF THE RATE-CONSTANT OF A CATALYTIC REACTION USING A PARALLEL INCIDENT SPECTROELECTROCHEMICAL CELL

The possibility of determining the rate constant of a catalytic reaction using a parallel incident spectroelectrochemical cell was investigated in this work. Various spectroelectrochemical techniques were examined, including single-potential-step chronoabsorptometry, single-potential-step open-circuit relaxation chronoabsorptometry and double-potential-step chronoabsorptometry. The values determined for the kinetics of the ferrocyanide-ascorbic acid system are in agreement with the reported values. The parallel incident method is much more sensitive than the normal transmission method and can be applied to systems which have smaller molar absorptivities, larger rate constants or lower concentrations.

Improvement of different source function expressions in SWAN model for the Bohai Sea

The simulating wave nearshore (SWAN) wave model has been widely used in coastal areas, lakes and estuaries. However, we found a poor agreement between modeling results and measurements in analyzing the chosen four typical cases when we used the default parameters of the source function formulas of the SWAN to make wave simulation for the Bohai Sea. Also, it was found that at the same wind process the simulated results of two wind generation expressions (Komen, Janssen) demonstrated a large difference. Further study showed that the proportionality coefficient alpha in linear growth term of wave growth source function plays an unperceived role in the process of wave development. Based on experiments and analysis, we thought that the coefficient alpha should change rather than be a constant. Therefore, the coefficient alpha changing with the variation of friction velocity U (*) was introduced into the linear growth term of wave growth source function. Four weather processes were adopted to validate the improvement in the linear growth term. The results from the improved coefficient alpha agree much better with the measurements than those from the default constant coefficient alpha. Furthermore, the large differences of results between Komen wind generation expression and Janssen wind generation expression were eliminated. We also experimented with the four weather processes to test the new white-capping mechanisms based on the cumulative steepness method. It was found that the parameters of the new white-capping mechanisms are not suitable for the Bohai Sea, but Alkyon's white-capping mechanisms can be applicable to the Bohai Sea after amendments, demonstrating that this improvement of parameter alpha can improve the simulated results of the Bohai Sea.

In vitro iron enrichment experiments in the Prydz Bay, the Southern Ocean: A test of the iron hypothesis

In "high nitrate, low chlorophyll" (HNLC) ocean regions, iron has been typically regarded as the limiting factor for phytoplankton production. This "iron hypothesis" needs to be tested in various oceanic environments to understand the role of iron in marine biological and biogeochemical processes. In this paper, three in vitro iron enrichment experiments were performed in Prydz Bay and at the Polar Front north of the Ross Sea, to study the role of iron on phytoplankton production. At the Polar Front of Ross Sea, iron addition significantly (P < 0.05, Student's t-test) stimulated phytoplankton growth. In Prydz Bay, however, both the iron treatments and the controls showed rapid phytoplankton growth, and no significant effect (P > 0.05, Student's t-test) as a consequence of iron addition was observed. These results confirmed the limiting role of iron in the Ross Sea and indicated that iron was not the primary factor limiting phytoplankton growth in Prydz Bay. Because the light environment for phytoplankton was enhanced in experimental bottles, light was assumed to be responsible for the rapid growth of phytoplankton in all treatments and to be the limiting factor controlling field phytoplankton growth in Prydz Bay. During the incubation experiments, nutrient consumption ratios also changed with the physiological status and the growth phases of phytoplankton cells. When phytoplankton growth was stimulated by iron addition, N was the first and Si was the last nutrient which absorption enhanced. The Si/N and Si/P consumption ratios of phytoplankton in the stationary and decay phases were significantly higher than those of rapidly growing phytoplankton. These findings were helpful for studies of the marine ecosystem and biogeochemistry in Prydz Bay, and were also valuable for biogeochemical studies of carbon and nutrients in various marine environments.

Application of Neomysis awatschensis as a standard marine toxicity test organism in China

The small mysid crustacean Neomysis awatschensis was collected in the west coast of Jiaozhou Bay, Qingdao, China in 1992 and acclimated and cultured in laboratory conditions since then. Standard acute toxicity tests using 4-6 d juvenile mysids of this species were conducted and the results were compared with Mysidopsis bahia, a standard toxicity test organism used in the US in terms of their sensitivities to reference toxins, as well as their taxonomy, morphology and geographic distributions. Because of its wide distribution along the Chinese coast, similar sensitivity to pollutants as M. bahia, short life history, small size and the case of handling, this study intended to use N. awatschensis as one of the standard marine organisms for toxicity testing in China. The species were applied to acute toxicity evaluations of drilling fluid and its additives I organotin TPT and toxic algae, and to chronic ( life cycle) toxicity assays of organotin TPT and a toxic dinofalgellate Alexandrium tamarense, respectively. Using N, awatschensis as a standard toxicity testing organism in marine pollution assessment in China is suggested.

Studies on the hemolytic activity of tentacle extracts of jellyfish Rhopilema esculentum Kishinouye: Application of orthogonal test

The present work is first reporting the hemolytic activity of venom from jellyfish Rhopilema esculentum Kishinouye extracted by different phosphate buffer solutions and incubated at different temperature according to the orthogonal test L6(1) x 3(6). Of the seven controllable independent variables, incubated temperature and phenylmethylsulfonyl fluoride (PMSF) had strongest effect on the hemolytic activity. (c) 2006 Elsevier B.V. All rights reserved.

地下水位上升造成的黄土远程滑坡形成机理与数值模拟研究

Based on field survey, laboratory testing and numerical modeling, engineering characteristics of undisturbed loess and the mechanism of long-runout loess landslides caused by underground water level rise, as well as the formation conditions and spatial distribution of landslides, are systematically studied and analyzed. Loess landslides at south Plateau of Jingyang County are mainly classified as flowslide, slide and fall. Flowslide is the main type characteristic of high velocity, long runout and multi-stages. The steep relief composed of loose structured loess-old aged soil serials and the rise of groundwater table are the predominant conditions for landslides in the study area. To study loess mechanic poperties and loess landslides mechanisims, isotropically and anisotropically consolidated undrained compression(ICU and ACU) tests and constant-deviator-drained compression (CQD) tests were carried out on undisturbed samples. The results of undrained compression tests performed at the in-situ stress level show that the soils are of consistently strain-softening in the stress-strain relations and cause high excess pore pressure. The steady-state line and the potential region of instability are obtained from ICU and ACU test results. A necessary condition for liquefaction is that the soil state initially lies in or is brought into the potential instability region. In addition, a strong strain-softening model is also formed. CQD tests demonstrate that the mobilized friction angle is far less than the steady-state angle and that the soil experiences undrained contractive failure suddenly at very small strains when its stress path during drained loading tries to cross the potential instability region，thus validates the proposed instability region. Based on the location of the region of potential instability and the stress state of slope soil, a method of static liquefaction analysis is proposed for loess landslides caused by rise in groundwater table. Compared with other liquefaction analysis methods, this method overcomes the limitations inherent in conventional slope stability method and undrained brittleness index method. Triaxial tests composed of constant water content (CW) and wetting tests at constant deviator stress are performed on undisturbed unsaturated samples. The stress-strain relation of CW tests takes on strain-hardening behavior; The results of wetting tests at constant deviator stress designed to study the mechanics of failure of unsaturated loess caused by an increase in the degree of saturation (wetting) shows that a contractive failure occurs in the undisturbed samples. On the basis of the above triaxial test results, the initiation of static liquefaction is presented for long-runout loess landslides caused by rise in groundwater table, that is, the loess slope soil gradually transfer from unsaturated to saturated state under the infiltration of irrigation. A contractive failure occurs in the local region at very small strain by increasing the pore-water pressure at constant deviator stresses under drained conditons. It is the contractive failrue resulting from rise of pore pressure that leads to high excess pore pressure in the neighbour soil which reduces shear resistance of soil. The neighbour soils also fail due to the rapid increase in pore-water pressure. Thus a connected failure surface is developed quickly and a flowslide occurs. Based on the saturated-unsaturated seepage theory, transient seepage is computed using the finite element method on loess slope under groundwater table rise. Pore-water pressure distribution for every time step after irrigation are obtained. The phreatic surface in the slope increases with the groundwater table. Pore-water pressure distribution within 8m above the phreatic surface changes very quickly，but the water content and pore water pressure in the region ranging from 8m above the phreatic surface up to ground surface is almost not affected and the matric suction usually is kept at 100～120 kPa. Based on the results of laboratory tests and seepage flow analysis, the development process of loess landslide is modeled considering groundwater table rise. The shearing plastic zone first occurs at the slope toe where the soil is soaked for long term during rise in groundwater table. As irrigation continues, the shearing plastic zone gradually extends to the interior soils, with the results that the tensile plastic zone occurs at the slope crown. As time goes on, both the shearing plastic zone and tensile plastic zone continue to extend. Then a connected plastic zone is formed and fowslide occurs. In comparision to laboratory test results, the results of numerical simulation quite well verify the presented mechanism of static liquefaction of long-runout loess landslides caused by rise in groundwater table.

填土边坡水文作用机理与破坏过程研究—以深圳羊宝地填土滑坡为例

A full understanding of failure mechanism, critical hydrological condition, and process of mobilization and deposition of a landslide is essential for optimal design of stabilization measure and forecasting of landslide hazard. This requires a quantitative study of hydrological response of a slope to rainfall through field monitoring, laboratory test and numerical modelling. At 13:40 on September 18, 2002, a fill slope failed following a period of prolonged rain in Shenzhen, resulting in 5 fatalities and 31 injuries. The failed mass with a volume about 2.5×104m3 traveled about 140m on level ground. Field monitoring, laboratory test, theoretical analysis and numerical modelling were carried out to undestand the hydrological response and failure mechanism of this fill slope. This thesis mainly focuses on the following aspects: (1) The hydrological responses and failure processes of slopes under rainfall infiltration were reviewed. Firstly, the factors influencing on the hydrological responses of slopes were analysed. Secondly, the change of stress state of slope soil and modelling methods of slope failure under rainfall infiltration were reviewed. (2) The characteristics of the Yangbaodi landslide and associated rainfall triggering the failure were presented. The failure was characterized by shallow flowslide, due to an increase of ground water table caused by rainfall infiltration. (3) A fully automated instrumentation was carried out to monitor rainfall, and saturated – unsaturated hydrological response of the fill slope, using a raingauge, piezometers, tensiometers and moisture probes. A conceptual hydrogeological model was presented based on field monitoring and borehole data. Analysis of monitoring data showed that the high pore water pressure in fill slope was caused by upward flow of semiconfined groundwater in the moderately decomposed granite. (4) Laboratory and in-situ testing was performed to study the physical and mechanical properties of fills. Isotropically consolidated undrained compression tests and anisotropically consolidated constant shear stress tests were carried out to understand the failure mechanism of the fill slope. It is indicated that loosely compacted soil is of strain-softening behaviour under undrained conditions, accompanied with a rapid increase in excess pore water pressure. In anisotropically consolidated constant shear stress tests, a very small axial strain was required to induce the failure and the excess pore water pressure increased quickly at failure. This indicated that static liquefaction caused by rise in groundwater table due to rainfall infiltration occurred. (5) The hydraulic conductivity of the highly and moderately decomposed granite was estimated using monitering data of pore water pressure. A saturated – unsaturated flow was modeled to study the hydrological response of the fill slope using rainfall records. It was observed that the lagged failure was due to the geological conditions and the discrepancy of hydraulic conductivity of slope soils. The hydraulic conductivity of moderately decomposed granite is relatively higher than the other materials, resulting in a semiconfied groundwater flow in the moderately decomposed granite, and subsequent upward flow into the upper fill layer. When the ground water table in the fill layer was increased to the critical state, the fill slope failed. (6) Numerical exercises were conducted to replay the failure process of the fill slope, based on field monitoring, laboratory and in-situ testing. It was found that the fill slope was mobilized by a rapid transfer of the concentrated shear stress. The movement of failure mass was characterized by viscosity fluid with a gradual increase in velocity. The failure process, including mobilization and subsequent movement and deposition, was studied using numerical methods.

Methane aromatization in the absence of an added oxidant and the bench scale reaction test

A bench scale reaction test for methane aromatization in the absence of an added oxidant was performed and its reaction result evaluated based on the carbon balance of the system. The result was compared with those obtained from the micro-reaction test to ensure the accuracy of the internal standard analyzing method employed in this paper. The catalytic performances of modified Mo/HZSM-5 catalysts were examined. It was found that pre-treatment by steam on HZSM-5 weakened the serious deposition of coke, and pre-impregnation of n-ethyl silicate on HZSM-5 could improve the conversion of CH4, but had little effect on coke formation. A low temperature activation procedure including pre-reduction of the catalyst with methane prevents the zeolite lattice from being seriously destroyed by high valence state Mo species when the Mo loading is high. It was suggested that Mo2C species detected by XRD spectra was the active phase for CH4 aromatization.