Browsing by Author "Vogl, Jochen"

An interlaboratory comparison (ILC) was organised to characterise 87 Sr/ 86 Sr isotope ratios in geological and industrial reference materials by applying the so‐called conventional method for determining 87 Sr/ 86 Sr isotope ratios. Four cements (VDZ 100a, VDZ 200a, VDZ 300a, IAG OPC‐1), one limestone (IAG CGL ML‐3) and one slate (IAG OU‐6) reference materials were selected, covering a wide range of naturally occurring Sr isotopic signatures. Thirteen laboratories received aliquots of these six reference materials together with a detailed technical protocol. The consensus values for the six reference materials and their associated measurement uncertainties were obtained by applying a Gaussian, linear mixed effects model fitted to all the measurement results. By combining the consensus values and their uncertainties with an uncertainty contribution for potential heterogeneity, reference values ranging from 0.708134 mol mol ‐1 to 0.729778 mol mol ‐1 were obtained with relative expanded uncertainties of ≤ 0.007 %. This study represents an ILC on conventional 87 Sr/ 86 Sr isotope ratios, within which metrological principles were considered and the compatibility of measurement results obtained by MC‐ICP‐MS and by MC‐TIMS is demonstrated. The materials characterised in this study can be used as reference materials for validation and quality control purposes and to estimate measurement uncertainties in conventional 87 Sr/ 86 Sr isotope ratio measurement.

In most chemical reactions, stable isotopes are fractionated in a mass-dependent manner, yielding correlated isotope ratios in elements with three or more stable isotopes. The proportionality between isotope ratios is set by the triple isotope fractionation exponent θ that can be determined precisely for, e.g., sulfur and oxygen by IRMS, but not for metal(loid) elements due to the lower precision of MC-ICP-MS analysis and smaller isotopic variations. Here, using Mg as a test case, we compute a complete metrologically robust uncertainty budget for apparent θ values and, with reference to this, present a new measurement approach that reduces uncertainty on θ values by 30%. This approach, namely, direct educt-product bracketing (sample-sample bracketing), allows apparent θ values of metal(loid) isotopes to be determined precisely enough to distinguish slopes in three-isotope space. For the example of Mg, we assess appropriate quality control standards for interference-to-signal ratios and report apparent θ values of carbonate-seawater pairs. We determined apparent θ values for marine biogenic carbonates, where the foraminifera Globorotalia menardii yields 0.514 ± 0.005 (2 SD), the coral Porites, 0.515 ± 0.006 (2 SD), and two specimens of the giant clam Tridacna gigas, 0.508 ± 0.007 (2 SD) and 0.509 ± 0.006 (2 SD), documenting differences in the uptake pathway of Mg among marine calcifiers. The capability to measure apparent θ values more precisely adds a new dimension to metal(loid) δ values, with the potential to allow us to resolve different modes of fractionation in industrial and natural processes.