ON THE SIGNIFICANCE OF WAVELENGTH POSITIONING ACCURACY IN MULTICOMPONENT ANALYSIS TECHNIQUES FOR THE CORRECTION OF LINE INTERFERENCES IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

The present paper reports some definite evidence for the significance of wavelength positioning accuracy in multicomponent analysis techniques for the correction of line interferences in inductively coupled plasma atomic emission spectrometry (ICP-AES). Using scanning spectrometers commercially available today, a large relative error, DELTA(A) may occur in the estimated analyte concentration, owing to wavelength positioning errors, unless a procedure for data processing can eliminate the problem of optical instability. The emphasis is on the effect of the positioning error (deltalambda) in a model scan, which is evaluated theoretically and determined experimentally. A quantitative relation between DELTA(A) and deltalambda, the peak distance, and the effective widths of the analysis and interfering lines is established under the assumption of Gaussian line profiles. The agreement between calculated and experimental DELTA(A) is also illustrated. The DELTA(A) originating from deltalambda is independent of the net analyte/interferent signal ratio; this contrasts with the situation for the positioning error (dlambda) in a sample scan, where DELTA(A) decreases with an increase in the ratio. Compared with dlambda, the effect of deltalambda is generally less significant.

WAVELENGTH POSITIONING ERRORS AND TRUE DETECTION LIMIT IN RELATION TO MULTICOMPONENT ANALYSIS TECHNIQUES FOR THE CORRECTION OF LINE INTERFERENCES IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

The present paper deals with the evaluation of the relative error (DELTA(A)) in estimated analyte concentrations originating from the wavelength positioning error in a sample scan when multicomponent analysis (MCA) techniques are used for correcting line interferences in inductively coupled plasma atomic emission spectrometry. In the theoretical part, a quantitative relation of DELTA(A) with the extent of line overlap, bandwidth and the magnitude of the positioning error is developed under the assumption of Gaussian line profiles. The measurements of eleven samples covering various typical line interferences showed that the calculated DELTA(A) generally agrees well with the experimental one. An expression of the true detection limit associated with MCA techniques was thus formulated. With MCA techniques, the determination of the analyte and interferent concentrations depend on each other while with conventional correction techniques, such as the three-point method, the estimate of interfering signals is independent of the analyte signals. Therefore. a given positioning error results in a larger DELTA(A) and hence a higher true detection limit in the case of MCA techniques than that in the case of conventional correction methods. although the latter could be a reasonable approximation of the former when the peak distance expressed in the effective width of the interfering line is larger than 0.4. In the light of the effect of wavelength positioning errors, MCA techniques have no advantages over conventional correction methods unless the former can bring an essential reduction ot the positioning error.

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.

Accurate measurement of carrier-envelope phase drift for infrared femtosecond laser pulses

A novel scheme to eliminate the artificial background phase jitter is proposed for measuring the carrier-envelope phase drift of tunable infrared femtosecond pulses from an OPA laser. Different from previous methods, a reference spectral interference measurement is performed, which reveals the artificial phase jitter in the measurement process, in addition to the normal f-to-2f interference measurement between the incident laser pulses and it second harmonic. By analyzing the interference fringes, the accurate CEP fluctuation of the incident pulses is obtained. (c) 2008 Optical Society of America

RESOLUTION OF CLOSELY SPACED LINES WITH KALMAN FILTERING IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

Effects of some factors on the performance of our Kalman filter in discrimination of closely spaced overlapping signals were investigated. The resolution power of the filter for overlapping lines can be strengthened by reduction of the step size in scans. The minimum peak separation of two lines which the Kalman filter can effectively handle generally equals two to three times the step size in scans. Significant difference between the profiles of the analysis and interfering lines and multiple lines from matrix in the spectral window of the analysis line are very helpful for the Kalman filter to discern closely spaced analysis and interfering signals correctly, which allow the filter well to resolve the line pair with very small peak distance or even the entirely coincident lines.

EVALUATION OF THE RELIABILITY OF KALMAN FILTERING RESULTS IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

This paper deals with the evaluation of the reliability of the analytical results obtained by Kalman filtering. Two criteria for evaluation were compared: one is based on the autocorrelation analysis of the innovation sequence, the so-called NAC criterion; the other is the innovations number, which actually is the autocorrelation coefficient of the innovation sequence at the initial wavelength. Both criteria allow compensation for the wavelength positioning errors in spectral scans, but there exists a difference in the way they work. The NAC criterion can provide information about the reliability of an individual result, which is very useful for the indication of unmodelled emissions, while the innovations number should be incorporated with the normalization of the innovations or seek the help of the sequence itself for the same purpose. The major limitation of the NAC criterion is that it does not allow the theoretical modelling of continuous backgrounds, which, however, is convenient in practical analysis and can be taken with the innovations number criterion.

EVALUATION OF THE EFFECT OF WAVELENGTH POSITIONING ERRORS ON KALMAN FILTERING RESULTS IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

This work evaluates the effect of wavelength positioning errors in spectral scans on analytical results when the Kalman filtering technique is used for the correction of line interferences in inductively coupled plasma atomic emission spectrometry (ICP-AES). The results show that a positioning accuracy of 0.1 pm is required in order to obtain accurate and precise estimates for analyte concentrations. The positioning error in sample scans is more crucial than that in model scans. The relative bias in measured analyte concentration originating from a positioning error in a sample scan increases linearly with an increase in the magnitude of the error and the peak distance of the overlapping lines, but is inversely proportional to the signal-to-background ratio. By the use of an optimization procedure for the positions of scans with the innovations number as the criterion, the wavelength positioning error can be reduced and, correspondingly, the accuracy and precision of analytical results improved.

IMPROVEMENT OF SELECTIVITY WITH NUMERICAL DERIVATIVE TECHNIQUES IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

One of the most attractive features of derivative spectrometry is its higher resolving power. In the present power, numerical derivative techniques are evaluated from the viewpoint of increase in selectivity, the latter being expressed in terms of the interferent equivalent concentration (IEC). Typical spectral interferences are covered, including flat background, sloped background, simple curved background and various types of line overlap with different overlapping degrees, which were defined as the ratio of the net interfering signal at the analysis wavelength to the peak signal of the interfering line. the IECs in the derivative spectra are decreased by one to two order of magnitudes compared to those in the original spectra, and in the most cases, assume values below the conventional detection limits. The overlapping degree is the dominant factor that determines whether an analysis line can be resolved from an interfering line with the derivative techniques. Generally, the second derivative technique is effective only for line overlap with an overlapping degree of less than 0.8. The effects of other factors such as line shape, data smoothing, step size and the intensity ratio of analyte to interferent on the performance of the derivative techniques are also discussed. All results are illustrated with practical examples.

Compact finite difference - Fourier spectral method for three-dimensional incompressible Navier-Stokes equations

A new compact finite difference-Fourier spectral hybrid method for solving the three dimensional incompressible Navier-Stokes equations is developed in the present paper. The fifth-order upwind compact finite difference schemes for the nonlinear convection terms in the physical space, and the sixth-order center compact schemes for the derivatives in spectral space are described, respectively. The fourth-order compact schemes in a single nine-point cell for solving the Helmholtz equations satisfied by the velocities and pressure in spectral space is derived and its preconditioned conjugate gradient iteration method is studied. The treatment of pressure boundary conditions and the three dimensional non-reflecting outflow boundary conditions are presented. Application to the vortex dislocation evolution in a three dimensional wake is also reported.

Spectral-line profile of turbulent gas

phases should be specified when the particle Reynolds number is higher than

Numerical study on heavy rigid particle motion in a plane wake flow by spectral element method

Experimental particle dispersion patterns in a plane wake flow at a high Reynolds number have been predicted numerically by discrete vortex method (Phys. Fluids A 1992; 4:2244-2251; Int. J. Multiphase Flow 2000; 26:1583-1607). To address the particle motion at a moderate Reynolds number, spectral element method is employed to provide an instantaneous wake flow field for particle dynamics equations, which are solved to make a detail classification of the patterns in relation to the Stokes and Froude numbers. It is found that particle motion features only depend on the Stokes number at a high Froude number and depend on both numbers at a low Froude number. A ratio of the Stokes number to squared Froude number is introduced and threshold values of this parameter are evaluated that delineate the different regions of particle behavior. The parameter describes approximately the gravitational settling velocity divided by the characteristic velocity of wake flow. In order to present effects of particle density but preserve rigid sphere, hollow sphere particle dynamics in the plane wake flow is investigated. The evolution of hollow particle motion patterns for the increase of equivalent particle density corresponds to that of solid particle motion patterns for the decrease of particle size. Although the thresholds change a little, the parameter can still make a good qualitative classification of particle motion patterns as the inner diameter changes.

Space-resolved spectral diagnosis of line-shaped laser-produced magnesium plasmas

Space-resolved spectra of line-shaped laser-produced magnesium plasmas in the normal direction of the target have been obtained using a pinhole crystal spectrograph. These spectra are treated by a spectrum analyzing code for obtaining the true spectra and fine structures of overlapped lines. The spatial distributions of electron temperature and density along the normal direction of the target surface have been obtained with different spectral diagnostic techniques. Especially, the electron density plateaus beyond the critical surface in line-shaped magnesium plasmas have been obtained with a fitting technique applied to the Stark-broadened Ly-alpha wings of hydrogenic ions. The difference of plasma parameters between those obtained by different diagnostic techniques is discussed. Other phenomena, such as plasma satellites, population inversion, etc., which are observed in magnesium plasmas, are also presented.

Spectral effects for an ultrashort pulse train propagating in a two-level atom medium

We investigate the spectra of a femtosecond pulse train propagating in a resonant two-level atom (TLA) medium. it is found that higher spectral components can be produced even for a 2 pi femtosecond pulse train. Furthermore, the spectral effects depend crucially on both the relative shift phi and the delay time tau between the successive pulses of the femtosecond pulse train.

Constrained high-order statistical blind deconvolution of spectral data

A constrained high-order statistical algorithm is proposed to blindly deconvolute the measured spectral data and estimate the response function of the instruments simultaneously. In this algorithm, no prior-knowledge is necessary except a proper length of the unit-impulse response. This length can be easily set to be the width of the narrowest spectral line by observing the measured data. The feasibility of this method has been demonstrated experimentally by the measured Raman and absorption spectral data.

Conical emission by femtosecond pulses with different spectral bandwidths

Conical emission (CE) has been investigated experimentally by laser pulses with different pulse durations and spectral bandwidths. The results show that the overall CE curve will shift as the varying of spectral bandwidth of pump laser pulse. But for pump laser pulses which have same spectral bandwidth but different pulse duration, the CE angles will be same at the spectral region close to the pump wavelength while will be different at the spectral region far away from the pump wavelength. We have also fitted the measured CE angles with X-wave model. The calculated curves and the measured CE curves match reasonably well. The best fits indicate that the group velocity of the filament pulse may be greatly controlled by controlling the spectral bandwidth of pump laser pulse. (C) 2008 Elsevier B.V. All rights reserved.