Anion-Specific Sulfur Isotope Analysis by Liquid Chromatography Coupled to Multicollector ICPMS

An accurate method has been developed to measure, in a single analytical run, δ³⁴S in sulfite, sulfate and thiosulfate in water samples by liquid chromatography combined with multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). The method is based on the anionic exchange separation of sulfur species prior to their online isotope ratio determination by MC-ICPMS. Mass bias correction was accomplished by a novel approach based on the addition of an internal sulfur-containing standard to the sample. This innovative approach was compared to the sample-standard bracketing procedure. On-column isotopic fractionation was observed and therefore corrected by external calibration. Isotopic ratios were calculated by linear regression slope (LRS), an advantageous method for transient signals, leading to a combined uncertainty of δ³⁴S below 0.25‰ and a reproducibility below 0.5‰ for the injection of 1 μg of S. The method was successfully applied to the measurement of δ³⁴S in synthetic solutions and environmental water samples. Matrix effects leading to δ³⁴S overestimation were observed for sulfate in some samples with high sodium/sulfate mass ratios. The developed analytical procedure simplifies the δ³⁴S analysis of liquid environmental samples since preparation steps are no longer required and allows the analysis of several sulfur-containing species in a single run.