Recent advances in monitoring technology have enabled high frequency, in-situ measurements of total phosphorus and total reactive phosphorus to be undertaken with high precision, whilst turbidity can provide an excellent surrogate for suspended sediment. Despite these measurements being fundamental to understanding the mechanisms and flow paths that deliver these constituents to river networks, there is a paucity of such data for headwater agricultural catchments. The aim of this paper is to deduce the dominant mechanisms for the delivery of fine sediment and phosphorus to an upland river network in the UK through characterisation of the temporal variability of hydrological fluxes, and associated soluble and particulate concentrations for the period spanning March 2012–February 2013. An assessment of the factors producing constituent hysteresis is undertaken following factor analysis (FA) on a suite of measured environmental variables representing the fluvial and wider catchment conditions prior to, and during catchment-wide hydrological events. Analysis indicates that suspended sediment is delivered to the fluvial system predominantly via rapidly responding pathways driven by event hydrology. However, evidence of complex, figure-of-eight hysteresis is observed following periods of hydrological quiescence, highlighting the importance of preparatory processes. Sediment delivery via a slow moving, probably sub-surface pathway does occur, albeit infrequently and during low magnitude events at the catchment outlet. Phosphorus is revealed to have a distinct hysteretic response to that of suspended sediment, with sub-surface pathways dominating. However, high magnitude events were observed to exhibit threshold-like behaviour, whereby activation and connection of usually disconnected depositional zones to the fluvial networks results in the movement of vast phosphorus fluxes. Multiple pathways are observed for particulate and soluble constituents, highlighting the challenges faced in mitigating the delivery of contaminant fluxes to headwater river systems.