Nn. Sesi et Gm. Hieftje, STUDIES INTO THE INTERELEMENT MATRIX EFFECT IN INDUCTIVELY-COUPLED PLASMA SPECTROMETRY, Spectrochimica acta, Part B: Atomic spectroscopy, 51(13), 1996, pp. 1601-1628
Radially-resolved maps of calcium atom and ion emission and calcium at
om and ion number densities have been obtained in the presence and abs
ence of several concomitant elements. These concomitants include cesiu
m, barium, lithium, aluminum, thallium, silver, magnesium and zinc. In
addition, maps of electron concentration, electron temperature and ga
s-kinetic temperature are given for an analyte-only (Ca) plasma. The f
indings suggest the interelement interference effect to be the result
of at least three major processes operating simultaneously: lateral-di
ffusion (i.e. particle-voratilization) changes, shifts in analyte-ioni
zation equilibrium, and differences in collisional excitation efficien
cy. Expanded lateral diffusion caused by enhanced particle volatility
explains the greater number of analyte species in the off-axis plasma
zones when an interferent is added to the sample. The combined concomi
tant-induced effects of expanded lateral diffusion and shift in ioniza
tion equilibrium can be used to describe a drop in analyte ion concent
ration that occurs in the central channel but with little or no change
in the Ca atom number density. Enhanced collisional excitation caused
by small increases in the plasma electron number density and electron
temperature result in elevated analyte emission intensities in some p
lasma zones. Also, a charge-transfer mechanism is described which migh
t result in the direct production and excitation of Ca ions from molec
ular analyte species.