BCR-0002

A simplified method using a single column of N,N,N',N'-tetraoctyl diglycolamide (TODGA) resin is developed for the separation of Sr, Nd and Hf with matrix and interference elements from geological samples, and for subsequent determination of their isotopic ratios by multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). The analytes of Sr, Nd and Hf are absorbed by the TODGA resin and eluted with 6 mol/L HNO₃, 1.2 mol/L HCl and 1 mol/L HNO₃-1.6 mol/L HF, respectively. The separation procedure is validated by the certified reference materials (CRMs) of BHVO-2, BCR-2 and AGV-2 with analyte recovery greater than 97%. The ratios are measured for ⁸⁷Sr/⁸⁶Sr, ¹⁴³Nd/¹⁴⁴Nd and ¹⁷⁶Hf/¹⁷⁷Hf and the mean values (2σ) are 0.703455 (16), 0.512977 (12) and 0.283108 (8) for BHVO-2, 0.705008 (18), 0.512633 (10) and 0.282878 (4) for BCR-2, and 0.703989 (20), 0.512791 (8) and 0.282982 (8) for AGV-2, which are consistent with the certified values.

The non-traditional stable strontium (Sr) isotopes have received increasing attention recently as new geochemical tracers for studying Sr isotopic fractionation and source identification. This has been attributed to the advancement in multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS), allows to determine precisely and simultaneously of the triple Sr isotopes. In this study, we applied a modified empirical external normalization (EEN) MC-ICPMS procedure for mass bias correction in Sr isotopic measurement using (92)Zr/(90)Zr. High-purity Zr Standard was spiked into sample solutions and the degree of fractionation was calculated off-line using an exponential law. The long-term external reproducibility for NIST SRM 987 δ(87)Sr and δ(88)Sr was better than 0.040‰ and 0.018‰ (2SD), respectively. The IAPSO standard seawater was used as a secondary standard to validate the analytical protocol and the absolute ratios measured were 0.709161±0.000018 for (87)Sr/(86)Sr, 0.177±0.021‰ for δ(87)Sr, and 0.370±0.026‰ for δ(88)Sr (2SD, n=7). These values are in good agreement with the literature data analyzed by thermal ionization mass spectrometry (TIMS) double spike technique. Rock standards, BHVO-2, BCR-2 and AGV-2 were also analyzed to validate the robustness of the methodology and showed identical results with literature data. Compared to previous (91)Zr/(90)Zr correction, we obtained improved results based on (92)Zr/(90)Zr, probably due to similar mass difference between (92)Zr/(90)Zr and measured Sr isotopes. The new analytical protocol presented in this study not only improves the analytical precision but also increases sample efficiency by omitting the use of the standard-sample bracketing (SSB) procedure.