Quantification of individual polysulfides in lab-scale and full-scale desulfurisation bioreactors

Environmental pollution caused by the combustion of fuel sources containing inorganic and organic sulfur compounds such as hydrogen sulfide (H2S) and thiols, is a global issue as it leads to SO2 emissions. To remove H2S from gas streams such as liquefied petroleum gas (LPG), biological processes can be applied. In these processes, polysulfide anions (S-x(2-)) play a significant role as they enhance the dissolution of H2S and act as intermediates in the biological oxidation of hydrogen sulfide ions to elemental sulfur. Despite their important role, the distribution of the various polysulfide species in full-scale biodesulfurisation systems has not yet been reported. With conventionally applied spectrophotometric analysis it is only possible to determine the total concentration of S-x(2-). Moreover, this method is very sensitive to matrix effects. In this paper, we apply a method that relies on the derivatisation of S-x(2-) to dimethyl polysulfanes. Owing to the instability of higher dimethyl polysulfanes (Me2S4 to Me2S8), standards are not commercially available and had to be prepared by us. We present a simplified quantification method for higher dimethyl polysulfanes by calculating high performance liquid chromatogaphy (HPLC) UV response factors based on the addition of internal standards. The method was subsequently used to assess the distribution of polysulfide anions in both a laboratory-scale and a full-scale biodesulfurisation unit. We found that the average chain length of polysulfides strongly depends on the process conditions and a maximum of 5.33 sulfur atoms per polysulfide molecule was measured. Results of this study are required by mechanistic and kinetic models that attempt to describe product selectivity of sulfide oxidising bioreactors.