Abstract

In this work, a method for the accurate and precise determination of the Ge isotope ratio in synthetic water and natural samples of geological origin using multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) with hydride generation was developed. The method was based on the liquid–liquid extraction of Ge to eliminate all elements affecting the generation of germanium hydrides. The standard-sample bracketing method was used to correct instrumental bias. Registration of analytical signal in time-resolved mode gave way to choose signals with best parameters and improved the precision of the results. Controlling the pH by using acetic buffer boosted the sensitivity by nearly five times in comparison to hydride generation methods suggested by other authors. The newly developed method is much simpler and quicker, does not need laborious Ge separation with ion-exchange resins, and thanks to its superior sensitivity, allows measurements of the Ge isotopic ratio in materials with relatively low Ge content. Delta values of the 74Ge/70Ge isotope ratio were measured in standard reference materials for which reference values were available in the GeoREM database. We demonstrated that the accuracy and precession of this method are equally good or better than methods proposed by other authors.

Highlights

  • The solution of the NIST SRM 3120a standard was measured on MC-ICPMS after sample introduction using a hydride generation (HG) system without any pretreatment

  • To check the applicability of the proposed HG-MC-ICPMS method for Ge isotope analysis after extraction with chloroform, Ge isotope ratios were measured in standard reference material NIST 3120a solutions, synthetic seawater samples spiked with NIST SRM 3120a, and geological reference materials (Table 6)

  • The main advantage and novelty of this method were the application of liquid−liquid extraction of Ge to eliminate all elements depressing the generation of germanium hydrides with no need of laborious Ge preseparation with ion-exchange resins

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Summary

Introduction

Due to several limitations in reliable measuring procedures, there are less than a dozen of published studies reporting natural variations of Ge isotopes.[7] The high ionization energy of germanium prevents the measurement of small samples (

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