SIMULTANEOUS DETERMINATION OF GUANINE, URIC-ACID, HYPOXANTHINE AND XANTHINE IN HUMAN PLASMA BY REVERSED-PHASE HIGH-PERFORMANCE LIQUID-CHROMATOGRAPHY WITH AMPEROMETRIC DETECTION

A reversed-phase high-performance liquid chromatographic method with amperometric detection is described for the separation and quantification of uric acid, guanine, hypoxanthine and xanthine. The isocratic separation of a standard mixture of the compounds was achieved in 5 min on a Spherisorb 5 C-18 reversed-phase column, with a mobile phase of NaH2PO4 (300 mmol dm(-3) pH 3.0)-methanol-acetonitrile-tetrahydrofuran (97.8 + 0.5 + 1.5 + 0.2). Uric acid, guanine, hypoxanthine and xanthine were completely separated, with detection limits in the range 2-20 pmol per injection. The effect of pH and the composition of the mobile phase on the separation are described. The hydrodynamic voltammograms of these compounds were recorded at a glassy carbon electrode. The linear range of the calibration graph for each compound was: uric acid; 1-5000 mu mol dm(-3); guanine, 0.5-2000 mu mol dm(-3); hypoxanthine, 0.1-500 mu mol dm(-3) and xanthine, 0.5-5000 mu mol dm(-3). The within- and between-day precision was good. The uric acid and hypoxanthine content in human plasma was measured using the proposed method. Good recoveries of uric acid (97.9-103%), hypoxanthine (98.0-99.2%), guanine (96.0-98.3%) and xanthine (96.0-102%) were obtained from human plasma. The results of electrochemical detection were in good agreement with those of UV detection.

RAPID-DETERMINATION OF KINETIC-PARAMETERS FOR THE ELECTROCATALYTIC REDUCTION OF DIOXYGEN BY VITAMIN-B12 ADSORBED ON GLASSY-CARBON ELECTRODE

In this paper, the electrochemical behavior of vitamin B-12, ie cyanocobalamin (abbr. VB12) in a weak acidic aqueous solution and adsorbed on glassy carbon (GC) surface (abbr. VB12(ad)/GC) in different pH buffer solutions have been described by using cyclic voltammetry (cv). It is found that VB12 and VB12(ad)/GC exhibit catalytic activity for the electroreduction of O2 according to two reduction peaks at -0.50 and -1.00 V vs. sce; but their electrocatalytic activity is very unstable. Based on the method of hydrodynamic amperometry [B. Miller and S. Bruckenstein, J. electrochem. Soc. 117, 1033 (1970)], some kinetic parameters for the electrocatalytic reduction of O2 by VB12(ad)/GC have been determined rapidly by using a linear rotation-scan method [Rongzhong Jiang and Shaojun Dong, Electrochim. Acta 35, 1451 (1990)]. These kinetic parameters indicate that the reduction of O2 on VB12(ad)/GC gives water predominantly in both potential ranges which correspond to those two reduction peaks. Possible reaction mechanisms have been suggested.

THE VISCOSITY BEHAVIOUR OF SEP BLOCK COPOLYMER SOLUTION DURING ITS MICELLIZATION

The viscosities of polystyrene-b-poly (ethylene/propylene) diblock copolymer in mixed solvent of n-octane and benzene were measured. The influences of the constitution of the mixed solvent, temperature and concentration were on the viscosity investigated. During the micellization the solution viscosity increases rapidly. The results are consistent with the study on the micellization by light scattering. The average mass of micelleswas measured and the hydrodynamic radius of gyrations were calculated.

SENSITIVE AMPEROMETRIC DETECTION OF GLUCOSE BY REVERSED PHASE LIQUID-CHROMATOGRAPHY AT A PRUSSIAN BLUE CHEMICALLY MODIFIED ELECTRODE OF NOVEL CONSTRUCTION

A new liquid chromatography electrochemical (LCEC) scheme for glucose sensing has been developed on the basis of a Prussian Blue chemically modified electrode (CME) of novel construction and characterized in terms of various experimental parameters by the flow injection analysis (FIA) technique. Unique hydrodynamic voltammograms were obtained for the first time at the CME in the flow-through amperometric detection of glucose, and subsequently both anodic and cathodic peaks could be expected on monitoring the operating potential in the modest positive or negative region. The unique pH dependence on the CME response towards glucose makes it perfectly compatible with conventional reversed phase liquid chromatography systems. On the basis of these features, practical application in glucose LCEC detection has been effectively performed; a linear response range over three orders of magnitude and a detection limit of subpicomole level were readily obtained. The capability of the established LCEC mode in the direct sensing of urinary glucose has been demonstrated.

LIQUID-CHROMATOGRAPHY AMPEROMETRIC DETECTION OF CARBOXYLIC-ACIDS AND PHENOLIC-ACIDS WITH A COPPER-BASED CHEMICALLY-MODIFIED ELECTRODE

A copper-based chemically-modified electrode has been constructed and characterized by various experimental parameters in flow-through amperometric detection of carboxylic acids and phenolic acids. Novel hydrodynamic voltamperograms were first obtained in flow-through amperometric detection with the Cu-based CME and subsequently negative and positive peaks were observed in a single chromatogram. This unique and flexible potential dependence could be of great benefit in chromatographic speciation and quantification. These observations suggest that the detector response was governed by the complexation reaction of copper ions with the solutes.

Modern changes of tidal troughs among the radial sand ridges in northern Jiangsu coastal zone

Using satellite images taken on different dates, GIS analysis of aerial photos, bathymetric maps and other field survey data, tidal troughs and major sand ridges in the northern Jiangsu coastal area were contrasted. The results show that there have been three types of movement or migration of tidal trough in this area: (1) Periodic and restricted, this type of trough usually developed along the beaches with immobile gully head as a result of the artificial dams and the swing range increased from gully head to the low reaches, so they have been obviously impacted by human activity and have longer swing periods; (2) Periodic and actively, this kind of trough, which swung with a fast rate and moved periodically on sand ridges, were mainly controlled by the swings of the host tidal troughs and hydrodynamic forces upon tidal sand ridge and influenced slightly by human constructions; (3) Steadily and slowly, they are the main tidal troughs with large scale and a steady orientation in this area and have slow lateral movement. The differences in migration mode of tidal trough shift result in different rates of migration and impact upon tidal sand ridges. Lateral accumulation on current tidal trough and deposition on abandoned tidal troughs are the two types of sedimentation of the tidal sand ridges formation. The whole radial sand ridge was generally prone to division and retreat although sand ridges fluctuated by the analysis of changes in talwegs of tidal troughs and shorelines of sand ridges.

Impact of Brunswick river mouth training walls on adjacent beaches, Brunswick heads, New South Wales, Australia

River training walls have been built at scores of locations along the NSW coast and their impacts on shoreline change are still not fully understood. In this study, the Brunswick River entrance and adjacent beaches are selected for examination of the impact of the construction of major training walls. Thirteen sets of aerial photographs taken between 1947 and 1994 are used in a CIS approach to accurately determine tire shoreline Position, beach contours and sand volumes, and their changes in both time and space, and then to assess the contribution of both tire structures and natural hydrodynamic conditions to large scale (years-decades and kilometres) beach changes. The impact of the training walls can be divided into four stages: natural conditions prior to their construction (pre 1959), major downdrift erosion and updrift accretion during and. following the construction of the walls in 1959 similar to 1962 and 1966. diminishing impact of the walls between 1966 and 1987, and finally no apparent impact between 1987 similar to 1994. The impact extends horizontally about 8 km updrift and 17 km downdrift, and temporally up to 25 years..

Manganese abnormity in holocene Sediments of the Bohai Sea

Manganese abnormity has been observed in the Holocene sediments of the mud area of Bohai Sea. On the basis of grain size, chemical composition, heavy mineral content and accelerator mass spectrometry (AMS) C-14 dating of foraminifer, relationships between manganese abnormity and sedimentation rates, material source, hydrodynamic conditions are probed. Manganese abnormity occurred during the Middle Holocene when sea level and sedimentation rates were higher than those at present. Sedimentary hiatus was not observed when material sources and hydrodynamic conditions were quite similar. Compared with the former period, the latter period showed a decrease in reduction environment and an inclination toward oxidation environment with high manganese content, whereas provenance and hydrodynamic conditions showed only a slight change. From the above observations, it can be concluded that correlation among manganese abnormity, material source, and hydrodynamic conditions is not obvious. Redox environment seems to be the key factor for manganese enrichment, which is mainly related to marine authigenic process.

A preliminary study on fingerprinting approach in marine sediment dynamics with the rare earth elements

Locating the quantitized natural sediment fingerprints is an important work for marine sediment dynamics study. The total of 146 sediment samples were collected from the Shelf of the East China Sea and five rivers, including Huanghe (Yellow), Changjiang (Yangtze), Qiantang, Ou and Min River. The sediment grain size and the contents of rare earth elements (REEs) were measured with laser particle size analyzer and ICP-MS technology. The results show that absolute REE content (Sigma REE) and the concentration ratio of light REEs to heavy REEs (L/HREE) are different in the sediments among those rivers. There are higher REE contents in being less than 2 m and 2-31 mu m fractions in the Changjiang Estuary surface sediments. The REE contents of bulk sediment are dominated by the corresponding values of those leading size-fractions. Sigma REE of sediment is higher close to the estuaries and declines seaward on the inner shelf of the East China Sea (ECS). The L/HREE ratio has a tendency of increase southward from 28 degrees N. Hydrodynamic conditions plays a predominate role on spacial distributions of the surficial sediment's REE parameters. In some situations, the currents tend to remove the coarser light grains from initial populations, as well as the deposit of the finer heavy mineral grains. In other situations, the currents will change the ratio of sediment constituents, such as ratio between silts and clays in the sediments. As a result, the various values of Sigma REE or L/HREE ratio in different bulk sediments are more affected by the change of size-fractions than source location. Under the long-term stable hydrodynamic environment, i.e., the East China Sea Shelf, new sediment transport model based on the size and density gradation concept may help to understand the spatial distribution patterns of REE parameters.

Validation of RADARSAT-2 fully polarimetric SAR measurements of ocean surface waves

C band RADARSAT-2 fully polarimetric (fine quad-polarization mode, HH+VV+HV+VH) synthetic aperture radar (SAR) images are used to validate ocean surface waves measurements using the polarimetric SAR wave retrieval algorithm, without estimating the complex hydrodynamic modulation transfer function, even under large radar incidence angles. The linearly polarized radar backscatter cross sections (RBCS) are first calculated with the copolarization (HH, VV) and cross-polarization (HV, VH) RBCS and the polarization orientation angle. Subsequently, in the azimuth direction, the vertically and linearly polarized RBCS are used to measure the wave slopes. In the range direction, we combine horizontally and vertically polarized RBCS to estimate wave slopes. Taken together, wave slope spectra can be derived using estimated wave slopes in azimuth and range directions. Wave parameters extracted from the resultant wave slope spectra are validated with colocated National Data Buoy Center (NDBC) buoy measurements (wave periods, wavelengths, wave directions, and significant wave heights) and are shown to be in good agreement.

Simulating a typhoon storm surge in the East Sea of China using a coupled model

A coupled numerical model with a 2' x 2' resolution grid has been developed and used to simulate five typical typhoon storm surges (5612, 7413, 7910, 8114, and 9711) in the East Sea of China. Three main driving forces have been considered in this coupled model: wave radiation stress, combined wave-current bottom shear stress and wave-state-dependent surface wind stress. This model has then been compared with in situ measurements of the storm set-up. The effect of different driving force components on the total storm surge has also been investigated. This study has found that the coupled model with high resolution is capable of simulating the five typical typhoons better than the uncoupled models, and that the wave-dependent surface wind stress plays an important role in typhoon storm surge-wave coupling in this area and can increase the storm set-up by 1 m. The study of the five typhoon cases has shown that the general coupling effects could increase storm set-up by 20-32%. Thus, it is suggested that to predict typhoon storm surges in the East Sea of China, a storm surge-wave coupled model be adopted. (C) 2008 National Natural Science Foundation of China and Chinese Academy of Sciences. Published by Elsevier Limited and Science in China Press. All rights reserved.

Numerical wave flume study on wave motion around submerged plates

Nonlinear interaction between surface waves and a submerged horizontal plate is investigated in the absorbed numerical wave flume developed based on the volume of fluid (VOF) method. The governing equations of the numerical model are the continuity equation and the Reynolds-Averaged Navier-Stokes (RANS) equations with the k-epsilon turbulence equations. Incident waves are generated by an absorbing wave-maker that eliminates the waves reflected from structures. Results are obtained for a range of parameters, with consideration of the condition under which the reflection coefficient becomes maximal and the transmission coefficient minimal. Wave breaking over the plate, vortex shedding downwave, and pulsating flow below the plate are observed. Time-averaged hydrodynamic force reveals a negative drift force. All these characteristics provide a reference for construction of submerged plate breakwaters.

Analysis on suspended sediment deposition rate for muddy coast of reclaimed land

A new expression for calculating suspended fine-sediment deposition rate is developed based on theoretic analysis and experiments. The resulting equation is applied to simulation of fine sediment deposition in the reclaimed land in the Hangzhou Bay, China. The hydrodynamic environment in this area is solved by use of a long wave model, which gives the 2D-velocity field and considers bathymetric changes due to fine sediment deposition. The expression is proved convenient to use in engineering practice, and the predicted deposition rate agrees with the annual data available from field measurements from the first year to the third year after the construction of the long groin as a reclaiming method.

STUDY ON THE FORMATIONAL MECHANISM OF THE NORTHERN YELLOW (HUANGHAI) SEA COLD WATER MASS(I)

A hydrodynamic-thermodynamic equation set was set up to reflect the formational mechanism and evolution of the Northern Yellow (Huanghai) Sea cold water mass (NYSCWM) and its density circulation. Appropriate mathematical physical models were established by using some physical postulations. An approximate analytic solution to expound the distributions of temperature and three-dimensional current velocity, which can be used to expound the formational mechanism of the NYSCWM and its density circulation is obtained by using the theory of boundary layer and perturbational analyses.

SUSPENDED SEDIMENT TRANSPORT IN THE OFFSHORE NEAR YANGTZE ESTUARY

Based on the Estuarine, Coastal and Ocean Modeling System with Sediments (ECOMSED) model, a 3-D hydrodynamic-transport numerical model was established for the offshore area near the Yangtze Estuary in the East China Sea. The hydrodynamic module was driven by tide and wind. Sediment module included sediment resuspension, transport and deposition of cohesive and non-cohesive sediment. The settling of cohesive sediment in the water column was modeled as a function of aggregation (flocculation) and deposition. The numerical results were compared with observation data for August, 2006. It shows that the sediment concentration reduces gradually from the seashore to the offshore area. Numerical results of concentration time series in the observation stations show two peaks and two valleys, according with the observation data. It is mainly affected by tidal current. The suspended sediment concentration is related to the tidal current during a tidal cycle, and the maximum concentration appears 1 h-4 h after the current maximum velocity has reached.