Several interactions between Al and the solid phase of soil influence Al buffering in soil solution. This work evaluated soils cultivated with Pinus taeda L. to determine Al forms in organic and mineral horizons using various extraction methods and to relate acidity with clay mineralogy.

Organic and mineral horizons of 10 soil profiles (up to 2.1 m deep) in southern Brazil were sampled. Organic horizons were separated into fresh, aged, and fermented/humified litter. The following Al extraction methods were utilized: 0.5 mol L^?1 pH 2.8 CuCl₂–Al complexed in organic matter; 1.0 mol L^?1 KCl–exchangeable Al; water–Al soluble in soil solution; HF concentrated?+?HNO₃ concentrated?+?H₂O₂ 30% (v/v)–total Al. Six sequential extractions were carried out to isolate different forms of amorphous minerals that can buffer Al on soil solution: 0.05 and 0.1 mol L^?1 sodium pyrophosphate; 0.1 and 0.2 mol L^?1 ammonium oxalate; 0.25 and 0.5 mol L^?1 NaOH. Samples of clay were also analyzed by XRD.

There was a clear effect of litter age on increasing total Al concentration. In the aged litter and fermented and/or humified litter, levels of total Al were 1.4 to 3.8 and 1.5 to 7.8 times greater than in fresh litter, respectively. The CuCl₂ method had higher Al extraction capacity than the KCl method for litter. The lowest Al–pyrophosphate values were observed in the Oxisol, which also had a predominance of gibbsite and the lowest levels of Al–KCl and Al–CuCl₂. There was an inverse relationship between degree of soil weathering and soluble and exchangeable Al in soils. Available Al increased with higher Si proportion in minerals of the clay fraction (2:1?>?1:1?>?0:1).

The worst scenario was soils with the combination of high soluble and exchangeable Al levels and high concentrations of amorphous forms of Al minerals. The best predictors of Al accumulation in the youngest litter horizon were extractions of amorphous minerals with pyrophosphate and NaOH. These extractors are normally used to predict the level of Al buffering in soils. Organic matter had less influence on Al dynamics in soils.