APPLICATION OF ULTRAMICROELECTRODES IN STUDIES OF HOMOGENEOUS CATALYTIC REACTIONS .2. A THEORY OF QUASI-1ST AND 2ND-ORDER HOMOGENEOUS CATALYTIC REACTIONS

The analytical expressions of quasi-first and second order homogeneous catalytic reactions with different diffusion coefficients at ultramicrodisk electrodes under steady state conditions are obtained by using the reaction layer concept. The method of treatment is simple and its physical meaning is clear. The relationship between the diffusion layer, reaction layer, the electrode dimension and the kinetic rate constant at an ultramicroelectrode is discussed and the factor effect on the reaction order is described. The order of a catalytic reaction at an ultramicroelectrode under steady state conditions is related not only to C(Z)*/C(O)* but also to the kinetic rate constant and the dimension of the ultramicroelectrode; thus the order of reaction can be controlled by the dimension of the ultramicroelectrode. The steady state voltammetry of the ultramicroelectrode is one of the most simple methods available to study the kinetics of fast catalytic reactions.

APPLICATION OF ULTRAMICROELECTRODES IN STUDIES OF HOMOGENEOUS CATALYTIC REACTIONS .3. THE CONDITION FOR QUASI-1ST AND 2ND-ORDER HOMOGENEOUS CATALYTIC REACTIONS AT ULTRAMICRODISK ELECTRODES IN THE STEADY-STATE

The conditions for quasi-first and second order homogeneous catalytic reactions and their variation with each other at an ultramicrodisk electrode in the steady state are discussed in this paper. The order of reaction can be controlled by changing the dimension of the ultramicroelectrode: the second order reaction can be changed to quasi-first by decreasing the dimension of the ultramicroelectrode. An example of this is given. The main factor effect on the reaction order is the dimension of the ultramicroelectrode. The K4Fe(CN)6-aminopyrine system is selected to confirm the theory, the experiments showing that the system is a second order reaction at a 432 mum microelectrode, and a quasi-first order reaction at a 19 mum ultramicroelectrode. The kinetic constant of the system can be determined by applying the previous theory of homogeneous catalytic reaction.

Enriched accumulation and biotransformation of selenium in the edible seaweed Laminaria japonica

Accumulations of selenium in kelp Laminaria japonica cultured in seawater was achieved by adding selenite (Na2SeO3) with or without N-P (NaNO3 + NaH2PO4) nutrients at different concentrations. Biotransformation of selenium in the kelp was investigated through measuring the selenium of biological samples and different biochemical fractionations. The results showed that the optimal selenite-enrichment concentration is 200 mg L-1, which can allow the kelp to accumulate a total selenium content from 0.51 +/- 0.15 to 26.23 +/- 3.12 mug g(-1) of fresh weight (fw). Selenium composition analysis of kelp (control group) showed that selenium is present as organic selenium, which is up to 86.22% of the total selenium, whereas inorganic selenium is barely 4.85%. When L. japonica was exposed for 56 h in seawater containing 200 mg L-1 Na2SeO3, the organic selenium was 16.70 mug g(-1) of fw (68.23%) and inorganic selenium was 4.71 mug g(-1) of fw (19.26%). The capability of accumulation of selenium was further enhanced by adding N-P nutrients to the selenite-enriched medium. Total selenium is increased to be 33.65 mug g(-1) of fw at optimal concentration of N-P nutrient (150 mg L-1 NaNO3 and 25 mg L-1 NaH2PO4), whereas the inorganic selenium was not increased and remained at 4.597 mug g(-1) of fw (13.36%), and the increased part of selenium was organic selenium. This implied that kelp L. japonica could effectively transform inorganic selenium into organic selenium through metabolism.

Effect of carbon source on growth and lipid accumulation in Chlorella sorokiniana GXNN01

Heterotrophic culture of microalgae to develop methods of increasing biomass productivity and storage lipids has brought new insight to commercial biodiesel production. To understand the relationship between heterotrophy and lipid production, the effects of carbon sources on the growth and lipid accumulation of Chlorella sorokiniana GXNN01 was studied. The alga exhibited an increased growth rate in response to the addition of carbon sources, which reached the stationary phase after 48 h at 30A degrees C. In addition, glucose and NaAc had a significant effect on the lipid accumulation during the early-stationary phase. Specifically, the lipid content was 0.237 +/- 0.026 g g(-1) cell dry weight and 0.272 +/- 0.041 g L-1 when glucose was used as the carbon source, whereas the lipid content reached 0.287 +/- 0.018 g g(-1) cell dry weight and 0.288 +/- 0.008 g L-1 when NaAc was used as the carbon source. The neutral lipid content was found to first decrease and then increase over time during the growth phase. A glucose concentration of 20 mmol L-1 gave the maximal lipid yield and the optimum harvest time was the early-stationary phase.

Effect of iron on growth and lipid accumulation in Chlorella vulgaris

The economic feasibility of algal mass culture for biodiesel production is enhanced by the increase in biomass productivity and storage lipids. Effect of iron on growth and lipid accumulation in marine microalgae Chlorella vulgaris were investigated. In experiment I, supplementing the growth media with chelated FeCl3 in the late growth phase increased the final cell density but did not induce lipid accumulation in cells. In experiment II, cells in the late-exponential growth phase were collected by centrifugation and re-inoculated into new media supplemented with five levels of Fe3+ concentration. Total lipid content in cultures supplemented with 1.2 x 10(-5) mol L-1 FeCl3 was up to 56.6% biomass by dry weight and was 3-7-fold that in other media supplemented with lower iron concentration. Moreover, a simple and rapid method determining the lipid accumulation in C. vulgaris with spectrofluorimetry was developed. (c) 2007 Elsevier Ltd. All rights reserved.

The Shandong mud wedge and post-glacial sediment accumulation in the Yellow Sea

Two well-defined deltaic sequences in the Bohai Sea and in the South Yellow Sea represent post-glacial accumulation of Yellow River-derived sediments. Another prominent depocenter on this epicontinental shelf, a pronounced clinoform in the North Yellow Sea, wraps around the northeastern and southeastern end of the Shandong Peninsula, extending into the South Yellow Sea. This Shandong mud wedge is 20 to 40 m thick and contains an estimated 300 km(3) of sediment. Radiocarbon dating, shallow seismic profiles, and regional sea-level history suggest that the mud wedge formed when the rate of post-glacial sea-level rise slackened and the summer monsoon intensified, at about 11 ka. Geomorphic configuration and mineralogical data indicate that present-day sediment deposited on the Shandong mud wedge comes not only from the Yellow River but also from coastal erosion and local rivers. Basin-wide circulation in the North Yellow Sea may transport and redistribute fine sediments into and out of the mud wedge.

Grain-size records at ODP site 1146 from the northern South China sea: Implications on the east Asian monsoon evolution since 20 Ma

273 samples from Ocean Drilling Program (ODP) Site 1146 in the northern South China Sea (SCS) were analyzed for grain-size distributions using grain-size class vs. standard deviation method and end-member modeling algorithm (EMMA) in order to investigate the evolution of the East Asian mon-soon since about 20 Ma. 10-19 mu m/1.3-2.4 mu m, the ratio of two grain-size populations with the highest variability through time was used to indicate East Asian winter monsoon intensity relative to summer monsoon. The mass accumulation rate of the coarsest end member EM1 (eolian), resulting from EMMA, can be used as a proxy of winter monsoon strength and Asian inland aridity, and the ratio of EM1/(EM2+EM3) as a proxy of winter monsoon intensity relative to summer monsoon. The combined proxies show that a profound enhancement of East Asian winter monsoon strength and winter monsoon intensity relative to summer monsoon occurred at about 8 Ma, and it is possible that the summer monsoon simultaneously intensified with winter monsoon at 3 Ma. Our results are well consistent with the previous studies in loess, eolian deposion in the Pacifc, radiolarians and planktonic foraminifera in the SCS. The phased uplift of the Himalaya-Tibetan Plateau may have played a significant role in strengthening the Asian monsoon at 8 Ma and 3 Ma.

Development of the East Asian summer monsoon: Evidence from the sediment record in the South China Sea since 8.5 Ma

128 samples from Ocean Drilling Program (ODP) Site 1143 in the southern South China Sea were analyzed for grain size, clay minerals, biogenic opal content and quartz in order to reconstruct changes in East Asian monsoon climate since 8.5 Ma. An abrupt change of terrigenous mass accumulation rate (MAR), clay mineral assemblage, median grain size and biogenic opal MAR about 5.2 Ma suggests that between 8.5-5.2 Ma the source of terrigenous sediment was mainly in the region of surface uplift and basaltic volcanism in southern Vietnam. A simple model of East Asian summer monsoon evolution was based on the clay/feldspar ratio, kaolinite/chlorite ratio and biogenic opal MAR. The summer monsoon has two periods of maximum strength at 8.5-7.6 Ma and 7.1-6.2 Ma. Subsequently, there was a relatively stable period at 6.2-3.5 Ma, continued intensification about 3.5-2.5 Ma, and gradually weakening after 2.5 Ma. Since I Ma the monsoon has intensified, with remarkable high-frequency and amplitude variability. Simultaneous increase in sedimentation rates at ODP Sites 1143, 1146 and 1148, as well as in MAR of terrigenous materials, quartz, feldspar and clay minerals at ODP Site 1143 at 3.5-2.5 Ma, may be the erosional response to both global climatic deterioration and the strengthening of the East Asian summer monsoon after about 3-4 Ma. (c) 2006 Elsevier B.V. All rights reserved.

Third-order Stokes wave solutions for interfacial internal waves in a three-layer density-stratified fluid

Interfacial internal waves in a three-layer density-stratified fluid are investigated using a singular method, and third-order asymptotic solutions of the velocity potentials and third-order Stokes wave solutions of the associated elevations of the interfacial waves are presented based on the small amplitude wave theory. as expected, the third-order solutions describe the third-order nonlinear modification and the third-order nonlinear interactions between the interfacial waves. The wave velocity depends on not only the wave number and the depth of each layer but also on the wave amplitude.

Determination of fractional energy loss of waves in nearshore waters using an improved high-order Boussinesq-type model

Fractional energy losses of waves due to wave breaking when passing over a submerged bar are studied systematically using a modified numerical code that is based on the high-order Boussinesq-type equations. The model is first tested by the additional experimental data, and the model's capability of simulating the wave transformation over both gentle slope and steep slope is demonstrated. Then, the model's breaking index is replaced and tested. The new breaking index, which is optimized from the several breaking indices, is not sensitive to the spatial grid length and includes the bottom slopes. Numerical tests show that the modified model with the new breaking index is more stable and efficient for the shallow-water wave breaking. Finally, the modified model is used to study the fractional energy losses for the regular waves propagating and breaking over a submerged bar. Our results have revealed that how the nonlinearity and the dispersion of the incident waves as well as the dimensionless bar height (normalized by water depth) dominate the fractional energy losses. It is also found that the bar slope (limited to gentle slopes that less than 1:10) and the dimensionless bar length (normalized by incident wave length) have negligible effects on the fractional energy losses.

Higher-order Boussinesq-type equations for interfacial waves in a two-fluid system

Interfacial waves propagating along the interface between a three-dimensional two-fluid system with a rigid upper boundary and an uneven bottom are considered. There is a light fluid layer overlying a heavier one in the system, and a small density difference exists between the two layers. A set of higher-order Boussinesq-type equations in terms of the depth-averaged velocities accounting for stronger nonlinearity are derived. When the small parameter measuring frequency dispersion keeping up to lower-order and full nonlinearity are considered, the equations include the Choi and Camassa's results (1999). The enhanced equations in terms of the depth-averaged velocities are obtained by applying the enhancement technique introduced by Madsen et al. (1991) and Schaffer and Madsen (1995a). It is noted that the equations derived from the present study include, as special cases, those obtained by Madsen and Schaffer (1998). By comparison with the dispersion relation of the linear Stokes waves, we found that the dispersion relation is more improved than Choi and Camassa's (1999) results, and the applicable scope of water depth is deeper.

Second-order Stokes solutions for internal waves in three-layer density-stratified fluid

In this paper, internal waves in three-layer stratified fluid are investigated by using a perturbation method, and the second-order asymptotic solutions of the velocity potentials and the second-order Stokes solutions of the associated elevations of the interfacial waves are presented based on the small amplitude wave theory. As expected, the first-order solutions are consistent with ordinary linear theoretical results, and the second-order solutions describe the second-order modification on the linear theory and the interactions between the two interfacial waves. Both the first-order and second-order solutions derived depend on the depths and densities of the three-layer fluid. It is also noted that the solutions obtained from the present work include the theoretical results derived by Umeyama as special cases.