High resolution (0.1 cm sampling interval) profiles of pH were obtained from some recent estuarine (Long Island Sound, Chesapeake Bay) and freshwater (Lake Erie) sediments and from laboratory microcosms containing homogenized Lake Erie sediment (both with and without tubificid oligochaetes) by incrementally processing a micro-pH electrode downward through the sediment. In all sediments examined, a local pH minimum occurred immediately below the oxidized zone. In estuarine sediments, a second deeper pH minimum was observed. The presence of tubificids prevented profound pH changes from developing in microcosm sediments treated with a layer of activated sewage sludge and resulted in more modest alterations of pH profile in microcosm sediments lacking such a layer. The technique used in this study is by no means limited to pH. In principal, any chemical species that can be directly determined by electrodes (e.g. 02, S(-2)) may be studied. Microelectrode techniques could be especially useful in the study of chemical gradients around animal burrows and in time series studies of whole core diagenesis.