Precise And Accurate Mass-Independent Chromium Isotope Measurement By Total Evaporation Mode On Thermal Ionization Mass Spectrometry (TE-TIMS) At 200 Ng Level

Abstract

Mass-independent chromium (Cr) isotope ratios measurements have been widely used in dating early solar system events and tracing the genetic relationships between different solar system, as well as terrestrial materials. Current analytical techniques need relatively large sample sizes, and this limits the application of Cr isotopes on precious mission return samples and some Cr-poor samples (e.g., BCR-2 with Cr contents of ~15 ppm). This paper reports a novel analytical method for mass-independent Cr isotopic ratios measurements using a Thermal Ionization Mass Spectrometer (TIMS) operated in total evaporation (TE) mode. A three-step cation column (AG 50W-X12 resin, 200−400 mesh) chemistry is used to purify Cr in various samples, including chondrites, basalts and peridotites, and the Cr yield is better than 92%. Residual organics from column resins is detrimental to Cr ionization on filaments, we demonstrate that this can be effectively removed by treating samples with H2O2 at 40 O C on hotplate. Single Cr measurements on rhenium filaments consume 15 to 20 ng of Cr and sustain 52 Cr of ~10V for 10 to 20 minutes. Generally, for one sample of 200 ng Cr, 10−15 ng repeated measurements can be made and 2-standard error precisions of ~ 0.05 and ~ 0.10 for ε 53 Cr and ε 54 Cr*, respectively can be achieved. The reproducibility (the 2standard deviation) for ε 53 Cr and ε 54 Cr is 0.05 and 0.07, respectively, tested by multiple measurements for DTS-2b (USGS dunite) and NWA 7734 (ordinary chondrite). Concentration and doping test (mainly for Fe) have also been conducted. These tests show that the Fe/Cr must be < 5 % and the measured 56 Fe/ 52 Cr<1 ‰ in order to achieve accurate ε 54 Cr. Finally, the ε 53 Cr and ε 54 Cr values measured by normal method on TIMS are systematically higher than those measured by total evaporation method on TIMS, which is potentially caused by non-kinetic massdependent fractionation during Cr evaporation and ionization on TIMS. The TE method could reduce this effect that may cause inaccurate massindependent Cr isotope data on TIMS.

Atomic spectrometry update: review of advances in atomic spectrometry and related techniques

“…Zhu et al 171 detailed a method for determining mass-independent Cr isotope variation. They used TIMS in total evaporation analysis mode following sample purification with a three stage column chromatography and subsequent heating with H 2 O 2 to remove residual organics.…”