Past metal mining has left a legacy of highly contaminated sediments representing a significant diffuse source of contamination to water bodies in the UK and worldwide. This paper presents the results of an integrated approach used to define the role of sediments in contributing to the dissolved lead (Pb) loading to surface water in a mining-impacted catchment. The Rookhope Burn catchment, northern England, UK is affected by historical mining and processing of lead ore. Quantitative geochemical loading determinations, measurements of interstitial water chemistry from the stream hyporheic zone and inundation tests of bank sediments were carried out. High concentrations of Pb in the sediments from the catchment, identified from the British Geological Survey Geochemical Baseline Survey of the Environment (GBASE) data, demonstrate both the impact of mineralisation and widespread historical mining. The results from stream water show that the stream Pb load increased in the lower part of the catchment, without any apparent or significant contribution of point sources of Pb to the stream. Relative to surface water, the interstitial water of the hyporheic zone contained high concentrations of dissolved Pb in the lower reaches of the Rookhope Burn catchment, downstream of a former mine washing plant. Concentrations of 56 μg l−1 of dissolved Pb in the interstitial water of the hyporheic zone may be a major cause of the deterioration of fish habitats in the stream and be regarded as a serious risk to the target of good ecological status as defined in the European Water Framework Directive. Inundation tests provide an indication that bank sediments have the potential to contribute dissolved Pb to surface water. The determination of Pb in the interstitial water and in the inundation water, taken with water Pb mass balance and sediment Pb distribution maps at the catchment scale, implicate the contaminated sediments as a large Pb supply to surface water. Assessment of these diffuse contaminant sources is critical for the successful management of mining-impacted catchments.