The fate of dissolved dimethylsulfoniopropionate (DMSP) in seawater: tracer studies using 35S-DMSP

Abstract

The algal osmolyte dimethylsulfoniopropionate (DMSP) is distributed globally in the marine euphotic zone, where it represents a major form of reduced sulfur. Previous investigations of DMSP cycling have focused mainly on its degradation to the volatile sulfur species dimethylsulfide (DMS) and little is known about the other possible fates of the sulfur. In this study 35S-DMSP was used to trace the biogeochemical fate of sulfur in the natural pool of dissolved DMSP in seawater. Dissolved 35S-DMSP added to seawater was degraded within hours, with the 35S partitioning into three major, relatively stable, operational pools: particulates, dissolved non-volatile degradation products (DNVS), and volatiles. The mean values for partitioning of DMSP obtained from 20 different seawater incubations were (in terms of sulfur): particulates (33%; range 6–85%;); DNVS (46%; range 21–74%); and volatiles (9%; range 2–21%). Oceanic water samples had lower incorporation of DMSP-S into particulates and higher incorporation into DNVS as compared with coastal-shelf samples. Transient accumulation of untransformed 35S-DMSP in bacteria accounted for some of the particulate 35S, but most of the cell-associated DMSP was rapidly transformed and the sulfur incorporated into relatively stable macromolecules. 35S-labeled DNVS accumulated steadily during DMSP metabolism and approximately half of this pool was confirmed to be sulfate, implying that oxidation of DMSP-sulfur takes place on time scales of minutes to hours. Volatile products were produced rapidly from 35S-DMSP, but most were consumed within 1–3 h. Experiments showed that methanethiol (MeSH) was the major volatile compound produced from tracer DMSP, with longer-lived DMS formed in lower amounts. Tracer additions of 35S-MeSH to seawater resulted in incorporation of sulfur into cellular macromolecules and DNVS, suggesting MeSH was an intermediate in the conversion of DMSP into these pools. Experiments with 35S-DMS revealed that turnover of DMS was much slower than for DMSP or MeSH, and the retention of the DMS-sulfur in particles was only a minor fraction of the total amount metabolized. The majority of the 35S-DMS was transformed into DNVS including sulfate. Temperature and DMSP concentration significantly affected the partitioning of sulfur during DMSP degradation, with lower temperatures and higher substrate concentrations causing a shift from particulate into volatile and non-volatile dissolved products. Our work demonstrates that natural turnover of dissolved DMSP results in minor net production of sulfur gases, and substantial production of previously unrecognized products (particulate and dissolved non-volatile sulfur). The main fates of DMSP are tied to assimilation and oxidation of the reduced sulfur by microorganisms, both of which may act as important controls on the production of climatically active DMS.