Abstract

In this work, a method for species-specific isotopic analysis of sulfur via capillary electrophoresis hyphenated on-line with multicollector ICP-MS (CE/MC-ICP-MS) was developed. Correction for the mass bias caused by instrumental mass discrimination was realized via external correction with multiple-injection sample-standard bracketing. By comparing the isotope ratio measurement results obtained using the newly developed on-line CE/MC-ICP-MS method with those obtained via traditional MC-ICP-MS measurement after analyte/matrix separation by anion exchange chromatography for isotopic reference materials and an in-house bracketing standard, the most suitable data evaluation method could be identified. The repeatability for the sulfate-δ34S value (calculated from 18 measurements of a standard conducted over seven measurement sessions) was 0.57‰ (2SD) and thereby only twice that obtained with off-line measurements (0.30‰, n = 68). As a proof of concept for analysis of samples with a real matrix, the determination of the sulfur isotopic composition of naturally present sulfate was performed for different river systems. The CE/MC-ICP-MS results thus obtained agreed with the corresponding off-line MC-ICP-MS results within the 2SD ranges, and the repeatability of consecutive δ34S measurements (n = 3) was between 0.3‰ and 1.3‰ (2SD). Finally, the isotopic analysis of two different S-species in a river water sample spiked with 2-pyridinesulfonic acid (PSA) was also accomplished.Graphical abstractThe CE/MC-ICP-MS method developed allows for species-specific S isotopic analysis in samples containing multiple species. Mass bias is corrected for by multiple-injection sample-standard bracketing, while the repeatability (2SD) of the resulting 34δ-values is <1‰.

Highlights

  • In many scientific fields, isotopic analysis can offer valuable information, e.g., for tracing the origin of minerals, Sebastian Faßbender and Katerina Rodiouchkina contributed to this work

  • S is an element of great interest because it is the only covalently bound constituent of proteins that can be analyzed for its isotopic composition by MC-ICP-MS

  • Systems like the Aridus, employed for bulk MC-ICP-MS measurements of sulfur, require high flow rates of gases and the aspirated liquid for reliable aerosol generation, which is incompatible with the capillary electrophoresis (CE)/ICP-MS interface

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Summary

Introduction

Isotopic analysis can offer valuable information, e.g., for tracing the origin of minerals, Sebastian Faßbender and Katerina Rodiouchkina contributed to this work. Liver diseases were shown to cause a small (

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