Mechanisms controlling the concentrations of free Al3+ and total Al in the soil solution from three podzolic soils were evaluated. Saturation indices (SI) were calculated for five mineral phases, but no single phase determined the Al3+ activity. E horizon samples were found to be undersaturated with respect to all phases. A more detailed equilibrium study indicated that formation of proto-imogolite sols was commonly possible in B horizon solutions with pH > 5. The poor relationship between pH and pAl3+ in the E and B1 horizons did not support control by exchange reactions with solid organic matter, although partial least square (PLS) regressions indicated importance of soil-exchangeable Al in the B and C horizons. It was concluded that in the E and most of the B1 horizon solutions, Al3+ activity is controlled by equilibrium with soluble organic acids which was supported by the PLS regressions. (C) 2000 Elsevier Science B.V.