Micro-organisms and manganese cycling in a seasonally stratified freshwater dam

This work describes investigations into the role that biotic and abiotic mechanisms play in the manganese redox cycle in a freshwater dam over a twelve month period. Enzymatic control of manganese oxidation was taking place with a temperature optimum of approx. 30°C. Manganese oxidation was only significant above about 19°C. The temperature and season play vital roles in determining the extent to which abiotic and microbial mechanisms contribute to manganese oxidation. Results showed that microbial catalysis is overwhelmingly responsible for manganese oxidation in the lower epilimnion from November to May. Significant abiotic catalysis (up to 25%) can occur in late summer/autumn when the water temperature is greatest. Mn(II) oxidation, pseudo-first order rate constants to 1.12 × 10²² M^?4 · d^?1 were measured while poisoned sample experiments confirmed the role of biological mediation. In winter, biological control could not occur because of the lower temperature of the water column. The measurement of “x” in MnO_x showed that higher manganese oxidation states were expected when the manganese oxidation rate was at a maximum and therefore when microbial activity was greatest. Direct microbial reduction of MnO_x in the water column was of much less significance. However, indirect reduction may have taken place through the reaction of MnO_x with sulfide. The results of this work have important implications for the design and operation of artificial destratification units for the control of manganese speciation.