Comparative contributions of solution geochemistry, microbial metabolism and aquatic photosynthesis to the development of high pH in ephemeral wetlands in South East Australia.

The development of alkaline conditions in lakes and wetlands is common but the process of alkalinisation is not well elaborated. In this study we investigated causes of the seasonal alkalinisation of ephemeral wetlands in the South East of South Australia where pH values above 10 are frequently observed. This research combined field observations, geochemical analysis of wetland sediment and surface water, with mesocosm studies under controlled conditions. The results revealed a complex interplay between a number of different processes. A primary cause was attributed to sequestration of CO2 from the water column by plant photosynthesis, coupled with slow diffusion of CO2 from the air which led to its depletion in the water. Abundant plant growth also modified the water chemistry via uptake of nutrient elements, in particular calcium and magnesium and increased carbonate alkalinity in the water. Assessment of field results and geochemical modeling showed that low Ca/(HCO3(-) and CO3(-2)) ratios in the water, coupled with carbonate mineral (calcite, Mg substituted calcite, dolomite) precipitation and evapoconcentration, create a high alkalinity and pH (>9) baseline in many wetlands. The high baseline pH is then further increased by CO2 depletion due to photosynthesis. We could find no evidence that reduction of sulfate to sulfides by sulfur-reducing bacteria significantly contributed to the very high pH conditions.