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Sr Isotope Analysis of Picogram-Level Samples by Thermal Ionization Mass Spectrometry Using a Highly Sensitive Silicotungstic Acid Emitter

Li, Chao-Feng, Chu, Zhu-Yin, Wang, Xuan-Ce, Guo, Jing-Hui, Wilde, Simon A
Analytical chemistry 2019 v.91 no.11 pp. 7288-7294
archaeology, basalt, hairs, ionization, isotopes, mass spectrometry, melting, mica, pyrite, resistors, strontium
Thermal ionization mass spectrometry (TIMS) has shown excellent analytical precision for Sr isotopic ratio analysis, even for small masses of material (0.5–10 ng). However, because of the sensitivity limit of TIMS, it is still not possible to obtain high precision ⁸⁷Sr/⁸⁶Sr isotope ratios for picogram-level sample sizes (30–100 pg) due to the lack of a highly sensitive emitter. This study is the first to employ a highly sensitive silicotungstic acid emitter to measure Sr isotopes at the picogram-level using TIMS. This emitter produces a 3-fold enhancement in the ionization efficiency of Sr and not only significantly reduces the required sample size but also has good external precision. Analyses of the NIST 987 standard yield an external reproducibility (2 RSD, n = 8) better than ±0.013% even for 30 pg of Sr. It is possible to yield an internal precision (2 RSE) of ±0.003% for 100 pg of sample using the default 10¹¹ Ohm feedback resistors. This method was verified by using a suite of silicate reference materials. Replicate digestions and analyses (n = 8) of the basalt standard BCR-2 (⁸⁷Sr/⁸⁶Sr = 0.704998 ± 0.000028, 2 SD) at the 326 ± 30 pg level demonstrates that good external reproducibility is reached on ultratrace level silicate samples. This method has a wide variety of potential applications for samples containing ultralow amounts of Sr in geoscience and archeological studies, such as single grains of mica, sphalerite, and pyrite, single mantle melt inclusions, precious extra-terrestrial materials, and human hair to name just a few.