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Here we evaluate the performance and limitations of two frequently used model-types to predict trace element solubility in soils: regression based "partition-relations" and thermodynamically based "multisurface models", for a large set of elements. For this purpose partition-relations were derived for As, Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, Sb, Se, V, Zn. The multi-surface model included aqueous speciation, mineral equilibria, sorption to organic matter, Fe/Al-(hydr)oxides and clay. Both approaches were evaluated by their application to independent data for a wide variety of conditions. We conclude that Freundlich-based partition-relations are robust predictors for most cations and can be used for independent soils, but within the environmental conditions of the data used for their derivation. The multisurface model is shown to be able to successfully predict solution concentrations over a wide range of conditions. Predicted trends for oxy-anions agree well for both approaches but with larger (random) deviations than for cations.

Agricultural soil acidification in China is known to be caused by the over-application of nitrogen (N) fertilizers, but the long-term impacts of different fertilization practices on intensive cropland soil acidification are largely unknown. Here, we further developed the soil acidification model VSD+ for intensive agricultural systems and validated it against observed data from three long-term fertilization experiments in China. The model simulated well the changes in soil pH and base saturation over the last 20 years. The validated model was adopted to quantify the contribution of N and base cation (BC) fluxes to soil acidification. The net NO leaching and NOinput accounted for 80% of the proton production under N application, whereas one-third of acid was produced by BC uptake when N was not applied. The simulated long-term (1990-2050) effects of different fertilizations on soil acidification showed that balanced N application combined with manure application avoids reduction of both soil pH and base saturation, while application of calcium nitrate and liming increases these two soil properties. Reducing NH input and NO leaching by optimizing N management and increasing BC inputs by manure application thus already seem to be effective approaches to mitigating soil acidification in intensive cropland systems.

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