Model-Based Analysis of the Long-Term Effects of Fertilization Management on Cropland Soil Acidification.

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 NO3- leaching and NO4+input 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 NH4+ input and NO3- 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.

Temporal variability in trace metal solubility in a paddy soil not reflected in uptake by rice (Oryza sativa L.).

Alternating flooding and drainage conditions have a strong influence on redox chemistry and the solubility of trace metals in paddy soils. However, current knowledge of how the effects of water management on trace metal solubility are linked to trace metal uptake by rice plants over time is still limited. Here, a field-contaminated paddy soil was subjected to two flooding and drainage cycles in a pot experiment with two rice plant cultivars, exhibiting either high or low Cd accumulation characteristics. Flooding led to a strong vertical gradient in the redox potential (Eh). The pH and Mn, Fe, and dissolved organic carbon concentrations increased with decreasing Eh and vice versa. During flooding, trace metal solubility decreased markedly, probably due to sulfide mineral precipitation. Despite its low solubility, the Cd content in rice grains exceeded the food quality standards for both cultivars. Trace metal contents in different rice plant tissues (roots, stem, and leaves) increased at a constant rate during the first flooding and drainage cycle but decreased after reaching a maximum during the second cycle. As such, the high temporal variability in trace metal solubility was not reflected in trace metal uptake by rice plants over time. This might be due to the presence of aerobic conditions and a consequent higher trace metal solubility near the root surface, even during flooding. Trace metal solubility in the rhizosphere should be considered when linking water management to trace metal uptake by rice over time.

Bioavailability pathways underlying zinc-induced avoidance behavior and reproduction toxicity in Lumbricus rubellus earthworms.

We investigated possible bioavailability pathways underlying zinc-induced avoidance behavior and sublethal reproduction impairment in Lumbricus rubellus. Clay-loam (pH 7.3) and sandy soil (three pH values of 4.3-6.0) were amended with zinc sulfate at six soil concentrations of total Zn ranging from 0.1 to 36 mmol/kg dw. Estimated and measured concentrations of free and exchangeable Zn ranged 10(-4) to 7.1 mmol/l. Avoidance behavior responses were fast and could be directly predicted from the activity of free zinc ions without a modifying pH effect. The repellent effect is thus likely mediated by a direct action of Zn(2+) ions on epidermal chemosensitive receptors. Body zinc uptake, however, was determined by proton competition with free Zn(2+) sorption. Excess accumulation of body Zn was a good predictor of reproduction decline, which is indicative of internal zinc poisoning. The results indicated that zinc affects earthworms via both direct and indirect mechanisms of external and internal exposure.

Modeling diffusive Cd and Zn contaminant emissions from soils to surface waters.

Modeling contaminant transport of diffusive contaminants is generally difficult, as most contaminants are located in the top soil where soil properties will vary strongly with depth and often a strong gradient in contaminant concentrations exists. When groundwater periodically penetrates the contaminated layers, stationary models (like most 3D models) cannot adequately describe contaminant transport. Therefore we have combined a hydrological instationary model using a 1D distributed column approach with a simple geochemical model to describe contaminant transport in the soil. Special to this model is that it includes lateral drainage from the soil column to different types of surface waters, which makes it possible to calculate surface water emissions especially for fluctuating groundwater tables. To test this model approach, we used it to quantify surface water emissions from soils in a catchment in the Kempen area which has been diffusively contaminated with Cd and Zn by zinc smelters. We ran the model for the period 1880-2000, starting with an uncontaminated soil in 1880. The model could describe both water discharge, surface water concentrations and current soil contents of Cd and Zn well. Further the model calculations showed that a stationary approach would underestimate leaching to surface waters considerably.

Evaluation of the performance and limitations of empirical partition-relations and process based multisurface models to predict trace element solubility in soils.

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.

Using advanced surface complexation models for modelling soil chemistry under forests: Solling forest, Germany.

Various dynamic soil chemistry models have been developed to gain insight into impacts of atmospheric deposition of sulphur, nitrogen and other elements on soil and soil solution chemistry. Sorption parameters for anions and cations are generally calibrated for each site, which hampers extrapolation in space and time. On the other hand, recently developed surface complexation models (SCMs) have been successful in predicting ion sorption for static systems using generic parameter sets. This study reports the inclusion of an assemblage of these SCMs in the dynamic soil chemistry model SMARTml and applies this model to a spruce forest site in Solling Germany. Parameters for SCMs were taken from generic datasets and not calibrated. Nevertheless, modelling results for major elements matched observations well. Further, trace metals were included in the model, also using the existing framework of SCMs. The model predicted sorption for most trace elements well.