A detailed investigation into sulphur leaching in peatland headwater catchments in the South Pennines, UK shows that, despite significant reductions in sulphur emissions, sulphur remains a key acidifier. This sulphur can be considered as legacy atmospheric pollution, stored within the peat by processes of dissimilatory sulphate reduction and now being leached into the region's surface waters. Persistently lower water tables at gully edge locations define a thick erosional acrotelm that is vulnerable to aeration, oxidation and flushing throughout the year, and not solely confined to periods of drought. Stream discharge behaves as a two-end member system, whereby pre-event water, rich in DOC and sulphate, is diluted by event water as a result of event water flowing through fast flow pathways such as macropores and overland flow. A rapid increase in water table elevation during the storm and a decrease in elevation after the storm indicate that event water has infiltrated the peat and has then been released into the stream. Streamwaters in peat dominated upland catchments with high densities of gullying have high concentrations of sulphate and low concentrations of DOC, whereas the reverse is true for those catchments with low densities of gullying. This is consistent with the concept that high concentrations of sulphate can suppress the solubility of DOC. A significant store of sulphate exists within South Pennine peats, and continued gully erosion will enhance sulphur leaching meaning that the timescale involved for any depletion is uncertain. It is therefore important that models predicting recovery from acidification in these upland systems include an understanding of how this stored sulphur is being leached, especially with respect to gully erosion, climate change and reduced precipitation. © 2008 Elsevier B.V. All rights reserved.