[Truncated abstract] The use of uncertainty analysis is gaining considerable attention in catchment hydrological modeling. In particular, the choice of an appropriate model structure, the identifiability of parameter values, and the reduction of model predictive uncertainty are deemed as essential elements of hydrological modelling. The chosen model structure must be parsimonious, and the parameters used must either be derivable from field measured data or inferred unambiguously from analysis of catchment response data. In this thesis, a long-term water balance model for the Susannah Brook catchment in Western Australia has been pursued using the ?downward approach?, which is a systematic approach to determine the model with the minimum level of complexity, with parameter values that in theory are derivable from existing physiographic data relating to the catchment. Through the analysis of the rainfall-runoff response at different timescales, and the exploration of the climate, soil and vegetation controls on the water balance response, an initial model structure was formulated, and a priori model parameter values estimated. Further investigation with the use of auxiliary data such as deuterium concentration in the stream and groundwater level data exposed inadequacies in the model structure. Two more model structures were then proposed and investigated through formulating alternative hypotheses regarding the underlying causes of observed variability, including those associated with the absence of a contribution of deep groundwater flow to the streamflow, which was indicated by deuterium concentration and internal dynamics characterized by the observed groundwater levels. ... These differences are due to differences in the time delay between rainfall and recharge between upland and riparian regions. The ages of water recharging the groundwater and discharging from the catchment were estimated by assuming a piston flow mechanism. In the deeper, upland soils, the age of recharging water was considerably larger than the unsaturated zone delay would suggest; a recharge response 16 days after an infiltration event may involve water as much as 160 days old. On the other hand, the delay and the age of recharging water were much lower in the shallow riparian zone. Where the upland zone contributes significantly to discharge, the predicted difference between the rainfall-discharge response time and the average age of discharging water can be significant.