Evaluation strategies and uncertainty calculation of isotope amount ratios measured by MC ICP-MS on the example of Sr

Publikationen: Beitrag in FachzeitschriftÜbersichtsartikel(peer-reviewed)

Autoren

Externe Organisationseinheiten

  • Universität für Bodenkultur Wien : Standort Tulln
  • Helmholtz-Centre for Materials and Coastal Research

Abstract

This paper critically reviews the state-of-the-art of isotope amount ratio measurements by solution-based multi-collector inductively coupled plasma mass spectrometry (MC ICP-MS) and presents guidelines for corresponding data reduction strategies and uncertainty assessments based on the example of n(87Sr)/n(86Sr) isotope ratios. This ratio shows variation attributable to natural radiogenic processes and mass-dependent fractionation. The applied calibration strategies can display these differences. In addition, a proper statement of uncertainty of measurement, including all relevant influence quantities, is a metrological prerequisite. A detailed instructive procedure for the calculation of combined uncertainties is presented for Sr isotope amount ratios using three different strategies of correction for instrumental isotopic fractionation (IIF): traditional internal correction, standard-sample bracketing, and a combination of both, using Zr as internal standard. Uncertainties are quantified by means of a Kragten spreadsheet approach, including the consideration of correlations between individual input parameters to the model equation. The resulting uncertainties are compared with uncertainties obtained from the partial derivatives approach and Monte Carlo propagation of distributions. We obtain relative expanded uncertainties (U rel; k = 2) of n(87Sr)/n(86Sr) of < 0.03 %, when normalization values are not propagated. A comprehensive propagation, including certified values and the internal normalization ratio in nature, increases relative expanded uncertainties by about factor two and the correction for IIF becomes the major contributor.

Details

OriginalspracheEnglisch
Seiten (von - bis)351-367
Seitenumfang17
FachzeitschriftAnalytical and bioanalytical chemistry
Jahrgang408.2016
Ausgabenummer2
Frühes Online-Datum15 Okt. 2015
DOIs
StatusVeröffentlicht - Jan. 2016