Monitoring variations of dimethyl sulfide and dimethylsulfoniopropionate in seawater and the atmosphere based on sequential vapor generation and ion molecule reaction mass spectrometry

Abstract

To monitor the fluctuations of dimethyl sulfur compounds at the seawater/atmosphere interface, an automated system was developed based on sequential injection analysis coupled with vapor generation–ion molecule reaction mass spectrometry (SIA-VG-IMRMS). Using this analytical system, dissolved dimethyl sulfide (DMS_aq) and dimethylsulfoniopropionate (DMSP), a precursor to DMS in seawater, were monitored together sequentially with atmospheric dimethyl sulfide (DMS_g). A shift from the equilibrium point between DMS_aq and DMS_g results in the emission of DMS to the atmosphere. Atmospheric DMS emitted from seawater plays an important role as a source of cloud condensation nuclei, which influences the oceanic climate. Water samples were taken periodically and dissolved DMS_aq was vaporized for analysis by IMRMS. After that, DMSP was hydrolyzed to DMS and acrylic acid, and analyzed in the same manner as DMS_aq. The vaporization behavior and hydrolysis of DMSP to DMS were investigated to optimize these conditions. Frequent (every 30 min) determination of the three components, DMS_aq/DMSP (nanomolar) and DMS_g (ppbv), was carried out by SIA-VG-IMRMS. Field analysis of the dimethyl sulfur compounds was undertaken at a coastal station, which succeeded in showing detailed variations of the compounds in a natural setting. Observed concentrations of the dimethyl sulfur compounds both in the atmosphere and seawater largely changed with time and similar variations were repeatedly observed over several days, suggesting diurnal variations in the DMS flux at the seawater/atmosphere interface.