Modelling of sorption experiments and seepage data of an Amazonian Ultisol subsoil under cropping fallow

The results of physico-chemical investigations of an Ultisol subsoil under a 2-year old fallow in eastern Amazonia are presented. Subsoil chemistry was studied using 4 different approaches: i) concentrations of H, Na, K, Ca, Mg, Mn, Al, and Fe in seepage water were measured under field conditions, ii) the equilibrium soil chemistry was studied in sequential batch experiments where the soil was treated with different solutions, iii) results of batch experiments were simulated with a chemical equilibrium model, and iv) the seepage data were calculated using selectivity coefficients obtained by modelling the batch experiments. The model included multiple cation exchange, precipitation/dissolution of Al(OH)₃ and inorganic complexation. Cation selectivity coefficients were pK_x/Ca^sel: X = Na: 0.3, K: 0.8, Mg: ?0.1, and Al: 0.4. The amount of cations sorbed ranged from ?0.2 to 2.0 (K), ?0.7 to 2.3 (Mg), ?1.6 to 1.8 (Ca), ?4.8 to 3.6 (Al) and 0.0 to 8.5 (Na) mmol_c kg^?1. The model predictions were good with values lying within 0.3 pH units (for the pH range 3.7 to 7.2), and 3% of CEC for individual cations. The most important proton buffer reaction seemed to be the dissolution of gibbsite and a large release of Al into the soil solution. When selectivity coefficients obtained by the modelling procedure were used to predict the field data for cation concentrations in the seepage water, they decreased in the following order: Na > K > Ca > Mg > Al. These calculated values were similar to the measured order: Na > Ca > K ≈ Mg > Al. Thus the options for managing these soils should be carefully chosen to avoid soil acidification which may result from inappropriate use of fertilizer during the cropping period.