Abstract
Dimethyl sulfide (DMS) is a trace gas produced in the ocean that plays an important role in climate and contributes to the Earths energy balance. DMS is a product of the enzymatic cleavage of dimethyl sulfoniopropionate (DMSP), which is produced by certain phytoplankton species and bacteria. Processes within the DMS/P cycles in the surface ocean are complex and vary with time and space. In the sea surface microlayer (SML), which is the interface between the ocean and the atmosphere, DMS concentration may be altered relative to subsurface water (SSW), by elevated biological activity, light intensity, and gas exchange. The aim of this thesis is to determine the importance of the SML in DMS/P dynamics and air-sea exchange by developing a more robust technique for SML sampling to better understand the dynamics of DMSP and DMS, and comparing their dynamics in the SML and SSW in coastal waters and the open ocean. In addition, the impact of warming and ocean acidification on DMS/P dynamics is investigated to determine how they will be impacted by future climate change.
To characterize DMS dynamics in the SML, a more effective method for sampling trace gases in the SML was developed (Chapter 2). The method is reliant on diffusion through a gas-permeable tube due to the concentration gradient. The floating tube was tested and calibrated under semi-controlled conditions using coastal water, where its reproducibility, accuracy and effectiveness were established. The potential benefits of this new technique for sampling trace gases in the SML include reduced loss of DMS to air. The higher reproducibility and accuracy compared to other techniques confirmed the potential of the floating tube technique for trace gas measurement in the SML.
The method developed in Chapter 2 was applied in sampling of DMS in the SML along a coastal-open ocean gradient (Chapter 3), and in various water masses of the open ocean (Chapter 4). In both chapters, DMSP and DMS dynamics were related to biological, biogeochemical, and physical properties of the SML and SSW. Sampling was conducted over 3 months at three different stations with different degrees of coastal and open water influence around Wellington, New Zealand in Chapter 3. DMSP was significantly enriched in the SML in most sampling events and DMSP and DMS enrichments were influenced by biological production and bacterial consumption. Overall, there was no temporal trends or coastal-offshore gradient in DMS or related biogeochemical variables in the SML. However, DMS concentration, and also DMS to DMSP ratio, were significantly correlated with solar radiation indicating a role for light as a determinant of DMSP and DMS in the SML. In open ocean waters around the Chatham Rise, east of New Zealand, the SML and SSW in water masses of different phytoplankton composition and biomass were sampled (Chapter 4). There was no chlorophyll a enrichment in the SML, and bacterial and DMSP enrichment were only apparent at one station, despite sampling within a phytoplankton bloom. Furthermore, there were no relationships between DMSP and phytoplankton biomass or community composition in the SML, although DMSP was negatively correlated with PAR. DMS was only significantly enriched in the SML at one station. DMS and DMSP concentrations were correlated in both SML and SSW, with the differing slopes attributed to DMS loss in the SML. Daily deck incubations were carried out to quantify DMSP and DMS processes in the SML, including the net effect of light on DMS/P, bacterial consumption of DMS/P and DMS production, and DMS air-sea flux. Air-sea flux was the main pathway with a DMS flux of 1.0-11.0 µmol m-2 d-1 that concurs with climatological predictions for the region. Excluding air-sea emission, biological DMS production was the dominant process in the SML relative to biological consumption and the net effect of light. SML DMS yield was not significantly different to that in the SSW, and consequently processes within the SML do not significantly affect regional DMS emissions.
The impact of ocean acidification and warming on DMSP and DMS concentrations was established for New Zealand coastal waters. Four mesocosm experiments, in which temperature and pH were manipulated to values projected for the years 2100 and 2150, were carried out over three years with the initial phytoplankton community differing in composition and bloom status (Chapter 6:). Temporal changes in DMSP and DMS were established and linked to changes in community composition and biogeochemistry. Results indicate that future warming may have greater influence on DMS production than ocean acidification. The observed reduction in DMSP at warmer temperatures was associated with changes in phytoplankton community, and in particular with a decrease in small flagellates. As nutrient availability also influenced the response this should also be considered in models of future DMS. Although DMS concentration decreased under future conditions of ocean acidification and higher temperature, this decrease was not as significant as reported by other studies.
The results in this thesis contribute to a better understanding of DMSP and DMS dynamics in the surface ocean. The floating tube method developed to sample DMS in the SML, will permit the study of DMS in the SML in various oceanic regions with improved accuracy. This technique may also have potential for measuring other trace gases in the SML. Application of this technique in coastal and open ocean waters demonstrated differences in DMS dynamics in the SML between these regions. DMS enrichment in the SML was rarely found, and DMS enrichment does not affect DMS air-sea flux significantly. Biological and biogeochemical variables and DMS/P process rates need to be established to further understanding of DMS/P dynamics in the SML and near surface water. Finally, results suggest that impacts of future climate change on DMS emissions may not be as significant as reported elsewhere, but that phytoplankton community composition plays a role and must be considered in future scenario models to better predict future DMS emissions.