AbstractMost sulphur diagenesis models predict that SO42‐ concentrations decrease exponentially with increasing sediment depth and are lower than that of the overlying water throughout the sediments. Low SO42‐ concentrations (less than 0.2 mM) are common in the sediments of Lake Anna that receive acid mine drainage; however, sediment with as much as 20 mM SO42‐ at about 20cm below the sediment surface is also seen in this section of the lake. A decision tree was proposed to investigate the cause of the high SO42‐ concentrations at depth (HSD) in the sediment. The first possibility proposed was that an increase in the quantity of groundwater flowing through Lake Anna sediments may increase groundwater advection of SO42‐ or oxygen which would induce sulphide oxidation. This hypothesis was tested by measuring groundwater flow. HSD profiles were found in a discrete region of the lake; however, stations having these profiles did not have higher groundwater flow than other sites sampled. Alternate explanations for the HSD profiles were that the region in which they occurred had: (1) unusual sediment chemical compositions; (2) a different source of regional groundwater, or (3) a lateral intrusion of high SO42‐ groundwater. There were no differences in sulphide and organic matter concentrations between the two regions. The area which has HSD in the sediment covers a large area in the middle of the lake, so it is unlikely that it has a unique source of regional groundwater. The third alternative was supported by the fact that in all three sample years, HSD stations were located in the preimpoundment stream channel, which is a likely lateral flow path for groundwater containing high SO42‐ concentrations.