The cycling of biogenic volatile sulfur compounds (VSCs) within marine and terrestrial ecosystems has been shown to play an integral role in atmospheric chemistry; by influencing global climate change through the creation of cloud condensation nuclei and controlling acid-base chemistry; as well as influencing sediment chemistry including the interactions with trace metals, particularly regarding iron sulfide formation. Despite this, the examination of VSCs within Australian coastal acid sulfate soils (ASS) is an unexplored area of research. As ASS in Australia occupy an area in excess of 9 M ha, there is a clear need for a greater understanding of the cycling of these compounds within such systems. This thesis looks at the concentrations of several VSCs within agricultural and undisturbed ASS on the east coast of Australia. Initial measurements of sulfur dioxide (SO2) were made using passive diffusion samplers, which were followed by two detailed field-based studies looking at the concentrations and fluxes of both SO2 and hydrogen sulfide (H2S) using flux-gradient micrometeorological techniques. These novel results indicated that this agricultural ASS was a substantial source of atmospheric H2S (0.036-0.056 gSm-2yr-1), and SO2 (0.095-0.31 gSm-2yr-1), with flux values equating to many other salt- and freshwater marshes and swamps. The flux data also suggested that the ASS could be a continual source of H2S which is photo-oxidised during the daytime to SO2. Measurements of both compounds showed separate, inverse correlations to temperature and moisture meteorological parameters indicating possible contributing and / or causal release factors. Further identification of these and other VSCs within ASS samplers was undertaken in the laboratory using gas chromatography in combination with solid-phase microextraction. Although SO2 and H2S were not discovered within the headspace samples, two other VSCs important in atmospheric sulfur cycling and trace metal geochemistry were quantified; dimethylsulfide (DMS; &gt 300??g/L) and ethanethiol (ESH &gt 4??g/L). The measurements of H2S, DMS and ESH are the first quantifications with Australian ASS, and they may be important for refining regional or local atmospheric sulfur budgets, as well as interpreting previous SO2 emissions from ASS. Ultimately this thesis further enhances our understanding of the cycling of VSCs within acid sulfate systems.

The cycling of biogenic volatile sulfur compounds (VSCs) within marine and terrestrial ecosystems has been shown to play an integral role in atmospheric chemistry; by influencing global climate change through the creation of cloud condensation nuclei and controlling acid-base chemistry; as well as influencing sediment chemistry including the interactions with trace metals, particularly regarding iron sulfide formation. Despite this, the examination of VSCs within Australian coastal acid sulfate soils (ASS) is an unexplored area of research. As ASS in Australia occupy an area in excess of 9 M ha, there is a clear need for a greater understanding of the cycling of these compounds within such systems. This thesis looks at the concentrations of several VSCs within agricultural and undisturbed ASS on the east coast of Australia. Initial measurements of sulfur dioxide (SO2) were made using passive diffusion samplers, which were followed by two detailed field-based studies looking at the concentrations and fluxes of both SO2 and hydrogen sulfide (H2S) using flux-gradient micrometeorological techniques. These novel results indicated that this agricultural ASS was a substantial source of atmospheric H2S (0.036-0.056 gSm-2yr-1), and SO2 (0.095-0.31 gSm-2yr-1), with flux values equating to many other salt- and freshwater marshes and swamps. The flux data also suggested that the ASS could be a continual source of H2S which is photo-oxidised during the daytime to SO2. Measurements of both compounds showed separate, inverse correlations to temperature and moisture meteorological parameters indicating possible contributing and / or causal release factors. Further identification of these and other VSCs within ASS samplers was undertaken in the laboratory using gas chromatography in combination with solid-phase microextraction. Although SO2 and H2S were not discovered within the headspace samples, two other VSCs important in atmospheric sulfur cycling and trace metal geochemistry were quantified; dimethylsulfide (DMS; &gt 300??g/L) and ethanethiol (ESH &gt 4??g/L). The measurements of H2S, DMS and ESH are the first quantifications with Australian ASS, and they may be important for refining regional or local atmospheric sulfur budgets, as well as interpreting previous SO2 emissions from ASS. Ultimately this thesis further enhances our understanding of the cycling of VSCs within acid sulfate systems.