Spatial and temporal variation in calcium and aluminum in northern hardwood forest floors

Acid rain results in losses of exchangeable base cations from soils, but the mechanism of base cation displacement from the forest floor is not clear, and has been hypothesized to involve mobilization of aluminum from the mineral soil. We attempted to test the hypothesis that losses of calcium from the forest floor were balanced by increases in Al in NewHampshire northern hardwoods. We measured exchangeable (six stands) and acid extractable (13 stands) Ca and Al in horizons of the forest floor over an interval of 15 years. Our sampling scheme was quite intensive, involving 50 or 60 blocks per stand, composited in groups of 10 for chemical analysis. Even at this level of effort, few stands exhibited changes large enough to be significant. Because of high spatial variability, differences would have had to be greater than about 50% to be statistically detectable. Differences in Ca and Al concentrations between Oi, Oe, Oa, and A horizons, however, were readily detected. Acid-extractable Al increased with depth, while Ca concentrations decreased; Ca-to-Al ratios decreased from 8.3 (charge basis) in the Oi to 0.2 in the A horizon. Therefore, a small change in sampling depth, or the inclusion of more or less A horizon material in the forest floor, could cause large differences in measured Ca and Al concentrations. To detect small changes in exchangeable cations over time would require sampling very intensively with careful control for comparability of horizons.