Non-linear signal response functions and their effects on the statistical and noise cancellation properties of isotope ratio measurements by multi-collector plasma mass spectrometry

A nebulizer-centric response function model of the analytical inductively coupled argon plasma ion source was used to investigate the statistical frequency distributions and noise reduction factors of simultaneously measured flicker noise limited isotope ion signals and their ratios. The response function model was extended by assuming i) a single gaussian distributed random noise source (nebulizer gas pressure fluctuations) and ii) the isotope ion signal response is a parabolic function of the nebulizer gas pressure. calculations of ion signal and signal ratio histograms were obtained by applying the statistical method of translation to the non-linear response function model of the plasma. Histograms of Ni, Cu, Pr, Tl and Pb isotope ion signals measured using a multi-collector plasma mass spectrometer were, without exception, negative skew. Histograms of the corresponding isotope ratios of Ni, Cu, Tl and Pb were either positive or negative skew. There was a complete agreement between the measured and model calculated histogram skew properties. bulizer-centric response function model was also used to investigate the effect of non-linear response functions on the effectiveness of noise cancellation by signal division. An alternative noise correction procedure suitable for parabolic signal response functions was derived and applied to measurements of isotope ratios of Cu, Ni, Pb and Tl. The largest noise reduction factors were always obtained when the non-linearity of the response functions was taken into account by the isotope ratio calculation. le applications of the nebulizer-centric response function model to other types of analytical instrumentation, large amplitude signal noise sources (e.g., lasers, pumped nebulizers) and analytical error in isotope ratio measurements by multi-collector plasma mass spectrometry are discussed.