The analysis of dimethylsulfide and dimethylsulfoniopropionate in sea ice: Dry-crushing and melting using stable isotope additions

Sea ice is thought to be an important source of the climate-active gas dimethylsulfide (DMS), since extremely high concentrations of its precursor dimethylsulfoniopropionate (DMSP) have been found associated with high algal biomass. Accurate measurements of DMS and associated compounds in sea ice were until now not possible due to difficulties associated with the unavoidable melting process before analysis. Here we present and evaluate two methods to analyze DMS and DMSP in sea-ice cores accurately. The first, describes the dry-crushing method, which has its focus on the volatile compound DMS. A sub-sample of deeply frozen (<−30 °C) ice is crushed in a stainless steel vessel and the released gas phase is analyzed directly for DMS. The remaining ice is subsequently analyzed for its total DMSP content. With this method, DMS and DMSP profiles can be resolved even in ice cores stored deeply frozen for two years. The second method, involves a melting procedure, during which the conversion of compounds is monitored by adding differently deuterated isotopes of DMS and DMSP. Natural concentrations and stable isotopes of DMS and DMSP are simultaneously analyzed on a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS). Loss and conversion rates of the artificial isotopes are used to reconstruct the original concentrations of DMS and DMSP in ice and give important information on potential dynamical processes in sea-ice communities. It is concluded that in stored cores, the dry-crushing method provides the best results when the aim of the study is to differentiate between DMS and DMSP. When direct processing and analysis of the samples is possible, the isotope-addition method has the potential of providing concentrations of all S-compounds, including dissolved and particulate fractions. Moreover, it is suitable for the determination of process rates within the S-cycle.