L.T.C. Bonten

Influence of pH on the redox chemistry of metal (hydr)oxides and organic matter in paddy soils

PurposeThe primary purpose of this study was to determine how flooding and draining cycles affect the redox chemistry of metal (hydr)oxides and organic matter in paddy soils and how the pH influences these processes. Our secondary purpose was to determine to what extent a geochemical thermodynamic equilibrium model can be used to predict the solubility of Mn and Fe during flooding and draining cycles in paddy soils.Material and methodsWe performed a carefully designed column experiment with two paddy soils with similar soil properties but contrasting pH. We monitored the redox potential (Eh) continuously and took soil solution samples regularly at four depths along the soil profile during two successive flooding and drainage cycles. To determine dominant mineral phases of Mn and Fe under equilibrium conditions, stability diagrams of Mn and Fe were constructed as a function of Eh and pH. Geochemical equilibrium model calculations were performed to identify Mn and Fe solubility-controlling minerals and to compare predicted total dissolved concentrations with their measured values.Results and discussionFlooding led to strong Eh gradients in the columns of both soils. In the acidic soil, pH increased with decreasing Eh and vice versa, whereas pH in the alkaline soil was buffered by CaCO3. In the acidic soil, Mn and Fe solubility increased during flooding due to reductive dissolution of their (hydr)oxides and decreased during drainage because of re-oxidation. In the alkaline soil, Mn and Fe solubility did not increase during flooding due to Mn(II) and Fe(II) precipitation as MnCO3, FeCO3, and FeS. The predicted levels of soluble Mn and Fe in the acidic soil were much higher than their measured values, but predictions and measurements were rather similar in the alkaline soil. This difference is likely due to kinetically limited reductive dissolution of Mn and Fe (hydr)oxides in the acidic soil. During flooding, the solubility of dissolved organic matter increased in both soils, probably because of reductive dissolution of Fe (hydr)oxides and the observed increase in pH.ConclusionsUnder alternating flooding and draining conditions, the pH greatly affected Mn and Fe solubility via influencing either reductive dissolution or carbonate formation. Comparison between measurements and geochemical equilibrium model predictions revealed that reductive dissolution of Mn and Fe (hydr)oxides was kinetically limited in the acidic soil. Therefore, when applying such models to systems with changing redox conditions, such rate-limiting reactions should be parameterized and implemented to enable more accurate predictions of Mn and Fe solubility.

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.

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.

A model to calculate effects of atmospheric deposition on soil acidification, eutrophication and carbon sequestration

Triggered by the steep decline in sulphur deposition in Europe and North America over the last decades, research and emission reduction policies have shifted from acidification to the effects of nitrogen (N) deposition and climate change on plant species diversity and carbon (C) sequestration in soils and biomass. Consequently, soil-ecosystem models need to include detailed descriptions of C and N processes, and ideally provide output that link to plant species diversity models. We describe an extension of the Very Simple Dynamic (VSD) model, called VSD+, which includes an explicit description of C and N turnover. Model simulations for three forest stands, which differ in N deposition and soil C/N ratios, show that VSD+?can well predict both trends and absolute values of NO3 and NH4 concentrations in soil and stream waters, soil C/N ratios and pH, which makes VSD+?suitable for providing input for plant species diversity models. Air pollution policies have shifted from acidification to eutrophication and climate change.VSD+ is a soil-chemical model that includes explicit C and N dynamics.The model adequately predicts NO3 concentrations, pH and C and N dynamics.Output of the model is suitable input for plant species diversity models.

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.

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.

Feasibility of coupled empirical and dynamic modeling to assess climate change and air pollution impacts on temperate forest vegetation of the eastern United States

Changes in climate and atmospheric nitrogen (N) deposition caused pronounced changes in soil conditions and habitat suitability for many plant species over the latter half of the previous century. Such changes are expected to continue in the future with anticipated further changing air temperature and precipitation that will likely influence the effects of N deposition. To investigate the potential long-term impacts of atmospheric N deposition on hardwood forest ecosystems in the eastern United States in the context of climate change, application of the coupled biogeochemical and vegetation community model VSD+PROPS was explored at three sites in New Hampshire, Virginia, and Tennessee. This represents the first application of VSD+PROPS to forest ecosystems in the United States. Climate change and elevated (above mid-19th century) N deposition were simulated to be important factors for determining habitat suitability. Although simulation results suggested that the suitability of these forests to support the continued presence of their characteristic understory plant species might decline by the year 2100, low data availability for building vegetation response models with PROPS resulted in uncertain results at the extremes of simulated N deposition. Future PROPS model development in the United States should focus on inclusion of additional foundational data or alternate candidate predictor variables to reduce these uncertainties.

Dynamic Geochemical Models to Assess Deposition Impacts and Target Loads of Acidity for Soils and Surface Waters

This chapter presents four geochemical dynamic models (VSD, MAGIC, ForSAFE and SMARTml) that have been used to assess impacts of nitrogen and acidity inputs on soil and soil solution chemistry. These models differ in their complexity and description of some processes. Some models can be used to calculate effects on surface waters as well. For all models this chapter shows examples of site-scale applications at intensively monitored forested plots in the UK, Germany, Switzerland and Norway, illustrating the adequacy of the model behaviour. Impacts of legislated emission reductions and forest harvest scenarios on soil solution chemistry are illustrated with a MAGIC model application. Besides scenario analyses, dynamic models can also be used to determine target loads, i.e. the deposition to reach a prescribed condition within a given time frame. This chapter introduces the target load concept and presents target load calculations with the MAGIC and the VSD model.

Integrated Assessment of Impacts of Atmospheric Deposition and Climate Change on Forest Ecosystem Services in Europe

Important forest ecosystem services are pollutant filtering relevant for an adequate water quality (regulating service), wood production (provisioning service) with related carbon (C) storage (regulating service) and the provision of a habitat for a diversity of plants and animals (supporting service). Nitrogen (N) and sulphur (S) deposition affect these ecosystem services. In this chapter, we describe the application of the soil model VSD, in combination with the forest growth model EUgrow and the plant species occurrence model PROPS to quantify the impact of N and S deposition on: (i) changes in soil buffering, in terms of accumulation or depletion of the pools of N, base cations (BC) and aluminium (Al), and changes in nitrate (NO3) and Al concentration in soil water, (ii) forest growth and carbon sequestration, and (iii) plant species diversity. Results showed that the depletion of Al and BC pools and the soil water concentrations of NO3 and Al increased strongly between 1950 and 1980, followed by a decrease between 1980 and 2010, reflecting the strong initial increase and subsequent decrease in N and S deposition in both periods, respectively. The impact of future emission reductions on the various parameters in the period 2010–2050 was larger than the climate change impact. Unlike soil and water quality, both N deposition and climate change had on average a positive impact on carbon sequestration. N deposition was calculated to be the dominant driver of changes in forest growth in the past (period 1900–2000) and climate change for the future (period 2000–2050). Plant species diversity changed hardly in scenarios assuming constant climate and low N deposition reduction, significantly at constant climate and strongly decreasing N deposition, and sharply when both climate and N deposition changed, especially in areas with a pronounced temperature change.