APPLICATION OF FACTOR-ANALYSIS TO CORRECTION OF SPECTRAL OVERLAP INTERFERENCE IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

Correction of spectral overlap interference in inductively coupled plasma atomic emission spectrometry by factor analysis is attempted. For the spectral overlap of two known lines, a data matrix can be composed from one or two pure spectra and a spectrum of the mixture. The data matrix is decomposed into a spectra matrix and a concentration matrix by target transformation factor analysis. The component concentration of interest in a binary mixture is obtained from the concentration matrix and interference from the other component is eliminated. This method is applied to correcting spectral interference of yttrium on the determination of copper and aluminium: satisfactory results are obtained. This method may also be applied to correcting spectral overlap interference for more than two lines. Like other methods of correcting spectral interferences, factor analysis can only be used for additive spectral overlap. Results obtained from measurements on copper/yttrium mixtures with different white noise added show that random errors in measurement data do not significantly affect the results of the correction method.

LEAST-SQUARES POLYNOMIAL SMOOTHING FOR INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTRA

The use of least-squres polynomial smoothing in ICP-AES is discussed and a method of points insertion into spectral scanning intervals is proposed in the present paper. Optimal FWHM/SR ratio can be obtained, and distortion of smoothed spectra can be avoided by use of the recommended method.

A hybrid coupled ocean-atmosphere model and ENSO prediction study

A hybrid coupled ocean-atmosphere model is designed, which consists of a global AGCM and a simple anomaly ocean model in the tropical Pacific. Retroactive experimental predictions initiated in each season from 1979 to 1994 are performed. Analyses indicate that: (1) The overall predictive capability of this model for SSTA over the central-eastern tropical Pacific can reach one year, and the error is not larger than 0.8 degrees C. (2) The prediction skill depends greatly on the season when forecasts start. However, the phenomenon of SPB (spring prediction barrier) is not found in the model. (3) The ensemble forecast method can effectively improve prediction results. A new initialization scheme is discussed.

Determination of tetrodotoxin by liquid chromatography coupled with electrospray ion-trap mass spectrometry

Two methods for tetrodotoxin analysis using liquid chromatography coupled with electrospray iontrap mass spectrometry (LC-ESI-MS) have been established with C,, reversed phase column and hydrophilic interaction liquid chromatography (HILIC) column, respectively. Sensitivity and reproducibility of the methods were compared. The method using C-18 column in selected ion monitoring (SIM) mode had a detection limit (S/N = 3) of 120 pg, and a good linearity of the calibration curve was obtained for tetrodotoxin (r = 0. 9992). High reproducibility of the method was observed, with a relative standard deviation (RSD) below 10%. The method using HILIC column in SIM mode and selected reaction monitoring (SRM) mode had detection limits (S/N = 3) of 15 and 3.75 pg, respectively. Good linearity of the calibration curves was obtained for tetrodotoxin (r = 0. 9996 and 0. 9998 in SIM and SRM mode, respectively). T he reproducibility was high in SIM mode but relatively poor in SRM mode. Based on the results, the method using HILIC column in SIM mode was suggested for the analysis of tetrodotoxin with LC-MS system.

Boundary Element Method (BEM) Analysis for Galvanic Corrosion of Hot Dip Galvanized Steel Immersed in Seawater

A numerical analysis of galvanic corrosion of hot-dip galvanized steel immersed in seawater was presented. The analysis was based on the boundary element methods (BEMs) coupled with Newton-Raphson iterative technique to treat the nonlinear boundary conditions, which were determined by the experimental polarization curves. Results showed that galvanic current density concentrates on the boundary of steel substrate and zinc coating, and the sacrificial protection of zinc coating to steel substrate results in overprotection of steel cathode. Not only oxygen reduction but also hydrogen reduction could occur as cathode reactions, which probably led up to the adsorption and absorption of hydrogen atoms. Flat galvanized steel tensile sample shows a brittle behavior similar to hydrogen embrittlement according to the SSRT (show strain rate test) in seawater.

Simultaneous Determination of Multi-Organotin Compounds in Seawater by Liquid-Liquid Extraction-High Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry

The hyphenated technique of high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (HPLC-ICP-MS) was applied to the simultaneous determination of five organotin compounds (trimethyltin, dibutyltin, tributyltin, diphenyltin and triphenyltin) in seawater samples. Agilent TC-C18 column was used for the separation, the mobile phase of HPLC was CH3CN : H2O: CH3COOH=65 : 23 : 12 (phi), 0.05% TEA, and pH value was adjusted to 3.0 by diluent ammonia. The flow rate was 0.6 mL . min(-1). Five mixed organotin compounds in a mix standard solution from 100 to 0.5 mu g . L-1 were applied for the method assessment. The experimental results indicate that the correlation coefficient of calibration curves (R-2) for each organotin compound was over 0.998 and the detection limits of the five organotin compounds were lower than 3 ng . L-1. Different mixed organic solvents including dichloromethane or toluene were used for extraction of organotin and the extraction condition of organotin from seawater was optimized. The 100 mL seawater acidized by hydrochloric acid was extracted by 10 mL carbon dichloride (CH2Cl2) with 2% tropolone for 10 min twice. Extracted organic solvents were mixed And blown to one drop by nitrogen with the rate of 1.7 mL . min(-1), then 1 mL acetonitrile was added to the drop for redissolving the organotin compounds. Finally, the mixed redissolution was filtered by 0.22 mu m organic filter membrane before analysis. it was found that the only organotin compound in seawater was triphenyltin (TPHT) and the content was 53.2 ng . L-1. The recoveries test from the standard addition for diphenyltin (DPHT), dibutyltin (DBT), tributyltin (TBT) and triphenyltin (TPHT) were over 80%. However, the recovery for trimethyltin (TMT) was relatively low and the value was 50%. The reason might be attributed to the decomposition or adsorption of those compounds during the extraction procedure. Further study on this subject is in progress.

Speciation Analysis of Organotin Compounds in Shellfish by Hyphenated Technique of High Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry

The hyphenated technique of high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry(HPLC-ICP-MS) was applied to the simultaneous determination of five organotin compounds in the shellfish samples. Agilent TC-C-18 column was selected, mobile phase of the HPLC was CH3CN:H2O: CH3COOH = 65:23:12 (V/V), 0. 05% TEA, pH = 3.0 at flow rate 0.4 mL/min. Five mixed organotin standards from 100 mu g/L to 0. 5 mu g/L was used for the method evaluation. The experimental results indicate that the linearity (R-2) for each compound was over 0.998. The shellfish samples were treated by supersonic extraction with mobile phase for 30min. Four organotin compounds including dibutyltin (DBT), tributyltin (TBT), diphenyltin (DphT) and triphenyltin (TPhT) in shellfish samples were detected with method mentioned above. It was found that the domain compounds in the samples were tributyltin (TBT) and triphenyltin (TPhT). The recoveries test from the standard addition for trimethyltin (TMT tributyltin (TBT), and triphenyltin (TPhT) were, over 80%. However, the recoveries for diphenyltin (DPhT) and dibutyltin (DBT) were relatively low, 37.3% and 75.2% respectively. The reason might be attributed to the decomposition of those compounds during the extraction procedure. The further study on this subject is under the progress.

The Coupled Depth/Slope Approach to Surface Reconstruction

Reconstructing a surface from sparse sensory data is a well known problem in computer vision. Early vision modules typically supply sparse depth, orientation and discontinuity information. The surface reconstruction module incorporates these sparse and possibly conflicting measurements of a surface into a consistent, dense depth map. The coupled depth/slope model developed here provides a novel computational solution to the surface reconstruction problem. This method explicitly computes dense slope representation as well as dense depth representations. This marked change from previous surface reconstruction algorithms allows a natural integration of orientation constraints into the surface description, a feature not easily incorporated into earlier algorithms. In addition, the coupled depth/ slope model generalizes to allow for varying amounts of smoothness at different locations on the surface. This computational model helps conceptualize the problem and leads to two possible implementations- analog and digital. The model can be implemented as an electrical or biological analog network since the only computations required at each locally connected node are averages, additions and subtractions. A parallel digital algorithm can be derived by using finite difference approximations. The resulting system of coupled equations can be solved iteratively on a mesh-pf-processors computer, such as the Connection Machine. Furthermore, concurrent multi-grid methods are designed to speed the convergence of this digital algorithm.

Determination of urinary nucleosides by direct injection and coupled-column high-performance liquid chromatography

A coupled-column liquid chromatographic method for the direct analysis of 14 urinary nucleosides is described. Efficient on-line clean-up and concentration of 14 nucleosides from urine samples were obtained by using a boronic acid-substituted silica column (40 turn x 4.0 mm I.D.) as the first column (Col-1) and a Hypersil ODS2 column (250 mm x 4.6 mm I.D.) as the second column (Col-2). The mobile phases applied consisted of 0.25 mol/L ammonium acetate (pH 8.5) on Col-1, and of 25 mmol/L potassium dihydrogen phosphate (pH 4.5) on Col-2, respectively. Determination of urinary nucleosides was performed on Col-2 column by using a linear gradient elution comprising 25 mmol/L potassium dihydrogen phosphate (pH 4.5) and methanol-water (60:40, v/v) with UV detection at 260 nm. Urinary nucleosides analysis can be carried out by this procedure in 50 min requiring only pH adjustment and the protein precipitation by centrifugation of urine samples. Calibration plots of 14 standard nucleosides showed excellent linearity (r > 0.995) and the limits of detection were at micromolar levels. Both of intra- and inter-day precisions of the method were better than 6.6% for direct determination of 14 nucleosides. The validated method was applied to quantify 14 nucleosides in 20 normal urines to establish reference ranges. (c) 2005 Elsevier B.V. All rights reserved.

Quantitative determination of compounds in tobacco essential oils by comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry

A quantitative analysis of the individual compounds in tobacco essential oils is performed by comprehensive two-dimensional gas chromatography (GC x GC) combined with flame ionization detector (FID). A time-of-flight mass spectrometer (TOF/MS) was coupled to GC x GC for the identification of the resolved peaks. The response of a flame ionization detector to different compound classes was calibrated using multiple internal standards. In total, 172 compounds were identified with good match and 61 compounds with high probability value were reliably quantified. For comparative purposes, the essential oil sample was also quantified by one-dimensional gas chromatography-mass spectrometry (GC/MS) with multiple internal standards method. The results showed that there was close agreement between the two analysis methods when the peak purity and match quality in one-dimensional GC/MS are high enough. (c) 2005 Elsevier B.V. All rights reserved.

Continuous configuration time-dependent self-consistent field method for polyatomic quantum dynamical problems

A new continuous configuration time-dependent self-consistent field method has been developed to study polyatomic dynamical problems by using the discrete variable representation for the reaction system, and applied to a reaction system coupled to a bath. The method is very efficient because the equations involved are as simple as those in the traditional single configuration approach, and can account for the correlations between the reaction system and bath modes rather well. (C) American Institute of Physics.

Two closely coupled lasers, dynamics & applications

The dynamics of two mutually coupled identical single-mode semi-conductor lasers are theoretically investigated. For small separation and large coupling between the lasers, symmetry-broken one-colour states are shown to be stable. In this case the light output of the lasers have significantly different intensities whilst at the same time the lasers are locked to a single common frequency. For intermediate coupling we observe stable two-colour states, where both single-mode lasers lase simultaneously at two optical frequencies which are separated by up to 150 GHz. For low coupling but possibly large separation, the frequency of the relaxation oscillations of the freerunning lasers defines the dynamics. Chaotic and quasi-periodic states are identified and shown to be stable. For weak coupling undamped relaxation oscillations dominate where each laser is locked to three or more odd number of colours spaced by the relaxation oscillation frequency. It is shown that the instabilities that lead to these states are directly connected to the two colour mechanism where the change in the number of optical colours due to a change in the plane of oscillation. At initial coupling, in-phase and anti-phase one colour states are shown to emerge from “on” uncoupled lasers using a perturbation method. Similarly symmetry-broken one-colour states come from considering one free-running laser initially “on” and the other laser initially “off”. The mechanism that leads to a bi-stability between in-phase and anti-phase one-colour states is understood. Due to an equivariant phase space symmetry of being able to exchange the identical lasers, a symmetric and symmetry-broken variant of all states mentioned above exists and is shown to be stable. Using a five dimensional model we identify the bifurcation structure which is responsible for the appearance of symmetric and symmetry-broken one-colour, symmetric and symmetry-broken two-colour, symmetric and symmetry-broken undamped relaxation oscillations, symmetric and symmetry-broken quasi-periodic, and symmetric and symmetry-broken chaotic states. As symmetry-broken states always exist in pairs, they naturally give rise to bi-stability. Several of these states show multistabilities between symmetric and symmetry-broken variants and among states. Three memory elements on the basis of bi-stabilities in one and two colour states for two coupled single-mode lasers are proposed. The switching performance of selected designs of optical memory elements is studied numerically.

Modelling the fluid dynamics and coupled phenomena in arc weld pools

A 3D model of melt pool created by a moving arc type heat sources has been developed. The model solves the equations of turbulent fluid flow, heat transfer and electromagnetic field to demonstrate the flow behaviour phase-change in the pool. The coupled effects of buoyancy, capillary (Marangoni) and electromagnetic (Lorentz) forces are included within an unstructured finite volume mesh environment. The movement of the welding arc along the workpiece is accomplished via a moving co-ordinator system. Additionally a method enabling movement of the weld pool surface by fluid convection is presented whereby the mesh in the liquid region is allowed to move through a free surface. The surface grid lines move to restore equilibrium at the end of each computational time step and interior grid points then adjust following the solution of a Laplace equation.

A two dimensional unstructured staggered mesh method with special treatment of tangential velocity

A two dimensional staggered unstructured discretisation scheme for the solution of fluid flow problems has been developed. This scheme stores and solves the velocity vector resolutes normal and parallel to each cell face and other scalar variables (pressure, temperature) are stored at cell centres. The coupled momentum; continuity and energy equations are solved, using the well known pressure correction algorithm SIMPLE. The method is tested for accuracy and convergence behaviour against standard cell-centre solutions in a number of benchmark problems: The Lid-Driven Cavity, Natural Convection in a Cavity and the Melting of Gallium in a rectangular domain.

Elemental analysis of soil samples for forensic purposes by inductively coupled plasma spectrometry - precision considerations

Major and trace elemental composition provides a powerful basis for forensic comparison of soils, sediments and rocks. However, it is important that the potential 'errors' associated with the procedures are fully understood and quantified, and that standard protocols are applied for sample preparation and analysis. This paper describes such a standard procedure and reports results both for instrumental measurement precision (repeatability) and overall 'method' precision (reproducibility). Results obtained both for certified reference materials and example soils show that the instrumental measurement precision (defined by the coefficient of variation, CV) for most elements is better than 2-3%. When different solutions were prepared from the same sample powder, and from different sub-sample powders prepared from the same parent sample, the CV increased to c. 5-6% for many elements. The largest variation was found in results for certified reference materials generated from 23 instrument runs over an 18 month period (mean CV=c. 11%). Some elements were more variable than others. W was found to be the most variable and the elements V, Cr, Co, Cu, Ni and Pb also showed higher than average variability. SiO2, CaO, Al2O3 and Fe2O3, Rb, Sr, La, Ce, Nd and Sm generally showed lower than average variability, and therefore provided the most reliable basis for inter-sample comparison. It is recommended that, whenever possible, samples relating to the same investigation should be analysed in the same sample run, or at least sequential runs.