High‐accuracy measurement of 36SF5+ signal using an ultrahigh‐resolution isotope ratio mass spectrometer

Abstract

RationaleThe Δ36S standard deviation measured in a conventional isotope ratio mass spectrometer such as MAT 253 is ca 0.1‰ to 0.3‰. At this precision, it is difficult to resolve the origin of non‐mass‐dependent sulfur isotope fractionation in tropospheric sulfate aerosol and in Martian meteorites or small deviations from the canonical mass‐dependent fractionation laws. Interfering ions with m/z at 131 of 36SF5+ are suggested by the community as the cause of the poor precision, but the exact ion species has not been identified or confirmed.MethodsHere we examined the potential interfering ions by using a Thermo Scientific ultrahigh‐resolution isotope ratio mass spectrometer to measure SF6 working gas and SF6 gases converted from IAEA‐S1/2/3 Ag2S reference materials.ResultsWe found that there are two resolvable peaks to the right of the 36SF5+ peak when a new filament was installed, which are 186WF42+ followed by 12C3F5+. However, only the 12C3F5+ interference peak was observed after more than three days of filament use. 12C3F5+ is generated inside the instrument during the ionization process. Avoiding the interfering signals, we were able to achieve a Δ36S standard deviation of 0.046‰ (n = 8) for SF6 zero‐enrichment and 0.069‰ (n = 8) for overall measurement start from silver sulfide IAEA‐S1.ConclusionsAging the filament with SF6 gas can avoid the interference of 186WF42+. Minimizing the presence of carbon‐bearing compounds and avoiding the interfering signals of 12C3F5+ from 36SF5+, we can improve Δ36S measurement accuracy and precision, which helps to open new territories for research using quadruple sulfur isotope composition.