Optimization of separation and MC-ICP-MS methods for determining Eu isotopic ratios in Si- and Ba-rich fractionated igneous rocks and other natural materials

Abstract

Eu isotope ratio can be precisely measured by MC-ICP-MS using a Sm isotope pair as spike for normalization. The standard chemical reagent NIST3117a exhibits almost no Eu isotope fractionation regardless of the kind of Sm isotope pairs used in normalization. However, Eu isotope fractionation can appear even in high purity Eu chemical reagents due to Gd and Ba impurities, interference with Sm isotope pair or use of different sample introduction methods. The Eu isotope fractionation in highly fractionated igneous rocks or feldspar minerals can arise from Gd and Ba impurities left by incomplete chemical separation. This study describes a modified, optimal method for accurately and precisely determining the degree of Eu isotope fractionation in highly fractionated Si-rich igneous rocks and Ba-rich feldspar. Ba oxide effects on Sm, Eu and Gd isotopes were monitored by MC-ICP-MS using different wet and dry plasma conditions for sample introduction. The Gd impurities exerts more influence than Ba impurities on Eu isotope ratios. The highly fractionated igneous rocks and feldspar materials showed consistent enrichment in the lighter Eu isotope (¹⁵¹Eu) which becomes a negative Eu isotopic value relative to NIST3117a. Results showed that highly purified Eu solutions from reagents containing no detectable Gd and Ba gave consistent Eu isotopic values regardless of Sm isotope pair (e.g., ¹⁴⁷Sm¹⁴⁹Sm, ¹⁴⁷Sm¹⁵²Sm, ¹⁴⁷Sm¹⁵⁴Sm, ¹⁴⁹Sm¹⁵⁴Sm, ¹⁵⁰Sm¹⁵⁴Sm) used in normalization. In order to obtain the best estimates of Eu isotope fractionation in different kinds of geological materials (including Si- and Ba-rich materials), Ba and Gd matrix must be completely removed and the Eu isotopic values calculated using four or more Sm spike isotope pairs.