Quantitative imaging of trace elements in solid samples by online isotope dilution laser ablation-inductively coupled plasma-mass spectrometry

For quantitative visualization of trace elements, an online isotope dilution (ID) laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) method capable of accurately correcting the detection amount of targets is presented. Two aerosols from an ablated sample and a nebulized isotopically enriched spike solution were mixed online using a dual-port spray chamber. In this paper, transmission efficiency (TE) of each of the two gas streams to the ICP-MS detector is revealed, and the quantification values were corrected by including the ratio of TEs in the calculation of the online ID method. To verify the developed method, Fe and Sr as model elements in five certified reference materials (CRMs, glass: SRM 610, 612, 614, alloy: SS-356, -383) were quantified without the use of matrix-matched CRMs. The resultant values agreed with the certified values of CRMs in the range of 92.7-104.7% and 92.8-109.0% for Fe and Sr, respectively. The LODs (3σ) were 0.54 and 0.17 μg g-1 for Fe and Sr, respectively. In addition, the applicability of this method to quantitative imaging of unknown solid samples was demonstrated for actual biological hard tissues (a mouse incisor, human primary tooth, and fish otolith) using the result of shot-analysis. The results were consistent with the reported concentration range obtained by wet chemical analysis.