Tree ring microanalysis by LA–ICP–MS for environmental monitoring: validation or refutation? Two case histories

An empirical approach is presented for validating trace metal profiles in tree rings for use as environmental archives. Concentration profiles of Zn, Cd, Cu, Pb and U in tree rings and lake sediments are compared for assessing the reliability of the former as an environmental proxy. Laser ablation sampling in conjunction with inductively coupled plasma mass spectrometry (LA-ICP-MS) is used for the direct analysis of tree rings. An optimised analytical protocol is devised with particular emphasis on sample preparation and quantification strategy. Significant correlations in the two environmental archives were found for zinc, copper and uranium, while cadmium and lead temporal trends, although showing enrichment in recent years, do not agree with the concentration profiles in lacustrine sediment cores. A chemical model based on metal affinity for hard type ligands present in wood is proposed to explain these results. Moreover, spring and winter wood are analysed separately thanks to the high spatial resolution of laser ablation sampling. As a result, enhanced metal loadings are shown to lead to intraring differences in trace metal concentrations.