A Method for Separation of Elemental Sulfur from Organic Polysulfides in Their Mixtures

Elemental sulfur frequently coexists with organic polysulfides in environmental samples and laboratory sulfurization experiments, complicating the accurate analysis of sulfur speciation. Reliable methods for selective sulfur removal are therefore required to avoid analytical artifacts. In this study, we systematically evaluated commonly used chemical sulfur removal approaches, including treatment with metallic copper and silver and reaction with tetrabutylammonium sulfite, and compared them with a chromatographic separation method based on C18 reversed-phase silica gel column chromatography. Model organic polysulfides, dimethyl polysulfides, diallyl polysulfides, dibenzyl disulfide, and cyclic polysulfide lenthionine were used to assess method performance under controlled conditions. The results demonstrate that chemical treatments are non-selective and lead to substantial decomposition of organic polysulfides, particularly for longer-chain compounds. In contrast, C18 reversed-phase silica gel column chromatography enables efficient and selective removal of elemental sulfur while preserving the original composition of organic polysulfides, with recoveries in the range of ~90–107%. These findings indicate that commonly applied sulfur removal procedures may introduce significant biases in sulfur speciation analyses. The chromatographic approach presented here provides a reproducible and non-destructive alternative for sample preparation, improving the reliability of studying sulfur speciation and transformation in natural and laboratory systems.