The centroid x 0 and the sigma values, i.e. (σ g ) left and (σ g ) right, of the central part of an experimental line profile in inductively coupled plasma emission spectrometry, which can be described by a Gaussian function, can be very useful for the detection of spectral interference. The methods of Boekelheide, Zimmermann, Mundschenk, Caruana et al., which can be used for the determination of these Gaussian parameters, are critically evaluated. The influence of statistical fluctuations on the accuracy of these parameters is studied using a Gaussian pseudo-random generator as described by Brent. It is shown that with the polynomials of Taylor and Schutyser, introduced for computer implementation of Boekelheide's method, no perfect linearization of the central part of a spectral line is obtained. It appears that with the expressions, proposed in this paper, more accurate full-width at half-maximum (FWHM) values can be obtained than with those of Taylor and Schutyser and, that they are better resistant to statistical fluctuations. Problems arise when the parameters of overlapping Gaussian distributions are to be determined since with Boekelheide's method the surface under each single Gaussian profile has to be known exactly a priori for the computation of the percentiles. It is found that with this method spectral interference can be detected only if two overlapping Gaussians are not too close (i.e. the difference of the centroids Δ x o≡( x o ) 1–( x o) 2 should exceed ca 0.5 FWHM). Zimmennann's method gives excellent results for the centroids and sigma values of Gaussian profiles and spectral interference can be detected fairly easily in most cases. The method has the additional advantage of performing well for relatively large statistical fluctuations. The method of Caruana et al. yields the same information as Zimmermann's procedure but appears to be more sensitive to statistical fluctuations especially when smaller fitting regions for the least-squares procedure are employed. Compared to Zimmermann's method it is, however, not so easy to detect spectral interference.
Read full abstract