[Truncated abstract] Pesticides are often transported to streams and/or groundwater as a result of the occurrence of rainfall events which trigger surface runoff or rapid preferential flow through the unsaturated zone. Much of the theory of solute transport has been derived assuming steady state or slowly varying upper boundary conditions and continuous, averaged process descriptions. However, a review of pesticide dynamics reveals that pesticides are episodically transported, predominantly through discrete flow pathways and this transport is often initiated as a near surface process, driven by naturally variable and intermittent rainfall intensities. The objective of the thesis is to better understand how the structure of natural variability of rainfall intensities impacts upon pesticide transport by these fast flow processes. We first conducted an analysis of a lysimeter leaching experiment that was aimed at identifying the rainfall controls on herbicide transport. Multivariate analyses revealed that average water balance behaviour at low temporal resolution controlled water and bromide transport while extreme rainfall events and rainfall event frequency controlled herbicide transport. A minimalist event based modelling approach was able to simulate the observed herbicide transport without or with only minor calibration. ... Finally we conduct a climate based regional risk assessment of pesticide leaching for the Wheatbelt region of the south-west of Western Australia. This is done for a suite of pesticides on a single soil to evaluate the impact of rainfall variability alone. Moderately sorbing, slowly degrading solutes have a greater regional potential for rapid leaching than both strongly and weakly sorbing solutes. High leaching potentials are found along the western and southern coast and in the far-east, with a band of low leaching potential through the central Wheatbelt. This is despite higher annual rainfall in the central areas compared to the east, and it is found that this occurs because of a change in the dominant fast flow triggers from frequent low intensity rainfall on the coasts to high intensity infrequent storms in the east. The coefficient of variation of annual leaching loads is similarly distributed. Spatial patterns of leaching potential depend upon chemical properties and application time. Peak loads of chemicals to fast flow pathways are found to converge to mid-winter, indicating periods of high loads of multiple pesticides may be an unavoidable consequence of the seasonality of storm properties.