Controlled dissolution for elemental analysis of sample layers by inductively coupled plasma-mass spectrometry: a feasibility study.

Aqueous acid mixtures at room temperature are used to partially dissolve steel samples. The dissolved elements are washed off the surface, diluted, and then determined by inductively coupled plasma-mass spectrometry (ICP-MS) using a magnetic sector mass analyzer. The amount of material removed is measured from the amount of Fe dissolved and increases linearly with HNO(3) concentration in the etch acid. Analyte concentrations in the solid are determined from the signal ratio of analyte ion/Fe(+). The shape of a plot of mass of element removed vs. nitric acid concentration yields information about the efficiency of the removal process and the likely chemical form of the element in the sample. For elements like Mn, Al, and W in steel, these plots have the same linear shape as that for the major element (Fe), and the measured concentrations agree well with the certified values. For problem elements like Nb and Ta, the plots have two linear regions with different slopes, and measured concentrations are lower than the certified values. Laser ablation ICP-MS and scanning electron microscopy (SEM) measurements show these elements to be associated together in the solid in refractory grains that are not dissolved to the same extent as the Fe matrix. For steel, the amount of Fe dissolved corresponds to an average depth of at least 4 microm, or 20 000 atomic layers.