Aluminium speciation in forest soil solution--modelling the contribution of low molecular weight organic acids

The concentrations of Al bound to identified low molecular weight organic acids (LMWOAs), phosphate and humic compounds in soil solutions (O1, O2, E, B1 and B2 horizons) from Fennoscandinavian coniferous forest soils were calculated. Two models were evaluated: WHAM (Winderemere Humic Aqueous Model) and a model treating the natural organic acids as monoprotic. The WHAM model was calibrated to find an average charge balance of unity, and then used for Al speciation. This was achieved considering approximately 80% of the natural fulvic acid to be 'active'. For the monoprotic model, constants obtained from previous fitting of soil solution data were used and the model was calibrated using acid/base titrations. The modelling confirms that the low molecular weight acids are important complex formers, binding on average 11-42% (O), 19-20% (E), and 0-30% (B) of the total Al in solution depending on the model used. The monoprotic model yielded higher concentrations than WHAM. Both models predicted that the major part of Al in solution was organically complexed to humic substances and LMWOAs, which was consistent with analytical values of 'quickly reacting' Al (monomenc inorganic forms; 12-14% of Al(tot) on average in the E and B1 solutions). Both models could predict the magnitude of the analytical values (RMSD = 4-5 microM). On average the WHAM model showed a better fit for the E horizon solutions and the monoprotic model for the upper B horizon. The pH dependence of the low molecular weight fraction of Al was modelled in the pH range 3-5.5 for a 'typical' O1 and E solution assuming no other changes in soil solution composition. The extrapolation showed that the models had a different pH dependence. The concentration of Al bound to LMWOAs in WHAM decreased with higher pH while the opposite was seen for the monoprotic model. Also the influence of the concentration of total Al in solution was modelled. The models showed similar trends but for the 'typical' O1 horizon sample the monoprotic model yielded higher concentrations of Al bound to LMWOAs than WHAM.