Elemental fractionation studies in laser ablation inductively coupled plasma mass spectrometry on laser-induced brass aerosols.

Previous investigations on laser-induced aerosols of brass samples showed that preferential vaporization of zinc occurs during the ablation process leading to elemental fractionation and limited possibilities for non matrix matched calibration. In a variety of experiments carried out within this study it is shown that multiple effects are complicating the quantification of brass using IA-ICPMS. It is shown that the ablated copper and zinc is not homogeneously distributed within the laser-produced aerosol. Copper was found enriched up to 100% in particles larger than 100 nm as shown from EDX measurements (electron excited) on individual particles, and zinc was enriched by over 40% in the particles smaller than the lowest measurable particle size (below 100 nm or in the vapor phase). Solution nebulization analysis on digested filter-collected aerosols results in a higher Cu/Zn ratio than the certified value for the brass sample. ESEM pictures with analysis of the electron excited X-rays measured on the filter-collected material support the results showing copper enrichment. However, online LA-ICPMS measurements carried out under the same operating conditions as for filtering show a copper depletion within the ICP, which leads to the conclusion of partial vaporization and ionization of the aerosol particles in the ICP. The larger particles containing more or exclusively copper are not completely ionized. Within this study, three sources of elemental fractionation can be distinguished and described: (A) The ablation process leads to no measurable copper enrichment at the ablation crater rim. (B) Zinc deposition between the ablation site and the aerosol collection on filters leads to an up to 37% higher Cu/Zn ratio on the filter in comparison to the certified value. (C) On-line laser ablation aerosols measured within the ICPMS lead to significantly lower Cu/Zn ratios in comparison to the certified value. (D) Combination of the various studied sources of fractionation can finally lead to an agreement between measured and certified values due to inverse overlapping of various fractionation sources.