La-Ce isotope measurements by multicollector-ICPMS

The ¹³⁸La-¹³⁸Ce decay system (half-life 1.02 × 10¹¹ years) is a potentially highly useful tool to unravel information about the timing of geological processes and about the interaction of geological reservoirs on earth, complementing information from the more popular ¹⁴⁷Sm-¹⁴³Nd and ¹⁷⁶Lu-¹⁷⁶Hf isotope systems. Previously published analytical protocols were limited to TIMS. Here we present for the first time an analytical protocol that employs MC-ICPMS, with an improved precision and sensitivity. To perform sufficiently accurate La-Ce measurements, an efficient ion-chromatographic procedure is required to separate Ce from the other rare earth elements (REE) and Ba quantitatively. This study presents an improved ion-chromatographic procedure that separates La and Ce from rock samples using a three-step column separation. After REE separation by cation exchange, Ce is separated employing an Ln Spec column and selective oxidation. In the last step, a cation clean-up chemistry is performed to remove all remaining interferences. Our MC-ICPMS measurement protocol includes all stable Ce isotopes (¹³⁶Ce, ¹³⁸Ce, ¹⁴⁰Ce and ¹⁴²Ce), by employing a 10¹⁰ ohm amplifier for the most abundant isotope ¹⁴⁰Ce. An external reproducibility of ±0.25ε-units (2 r.s.d) has been routinely achieved for ¹³⁸Ce measurements for as little as 150-600 ng Ce, depending on the sample-skimmer cone combinations being used. Because the traditionally used JMC-304 Ce reference material is not commercially available anymore, a new reference material was prepared from AMES laboratory Ce metal (Cologne-AMES). In order to compare the new material with the previously reported isotopic composition of AMES material prepared at Mainz (Mainz-AMES), Cologne-AMES and JMC-304 were measured relative to each other in the same analytical session, demonstrating isotope heterogeneity between the two AMES and different JMC-304 batches used in the literature. To enable sufficiently precise age correction of radiogenic ¹³⁸Ce and to perform isochron dating, a protocol was developed where La and Ce concentrations are determined by isotope dilution (ID), using an isotope tracer enriched in ¹³⁸La and ¹⁴²Ce. The new protocols were applied to determine the variations of Ce isotope compositions and La-Ce concentrations of certified geochemical reference materials (CRMs): BCR-2, BCR-1, BHVO-2, JR-1, JA-2, JB-3, JG-1, JR-1, JB-1b, AGV-1 and one in-house La Palma standard.