Plant species occurrence in Europe is affected by changes in nitrogen deposition and climate. Insight into potential future effects of those changes can be derived by a model approach based on field-based empirical evidence on a continental scale. In this paper, we present a newly developed empirical model PROPS, predicting the occurrence probabilities of plant species in response to a combination of climatic factors, nitrogen deposition and soil properties. Parameters included were temperature, precipitation, nitrogen deposition, soil pH and soil C/N ratio. The PROPS model was fitted to plant species occurrence data of about 800,000 European relevés with estimated values for pH and soil C/N ratio and interpolated climate and modelled N deposition data obtained from the Ensemble meteo data set and EMEP model results, respectively. The model was validated on an independent data set. The test of ten species against field data gave an average Pearson's r-value of 0.79. PROPS was applied to a grassland and a heathland site to evaluate the effect of scenarios for nitrogen deposition and climate change on the Habitat Suitability Index (HSI), being the average of the relative probabilities, compared to the maximum probability, of all target species in a habitat. Results for the period 1930-2050 showed that an initial increase and later decrease in nitrogen deposition led to a pronounced decrease in HSI, and with dropping nitrogen deposition to an increase of the HSI. The effect of climate change appeared to be limited, resulting in a slight increase in HSI.

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.

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.

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.

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. (C) 2016 Elsevier Ltd. All rights reserved.

Uptake of trace metals by crops is determined by the solubility of trace metals. In paddy soils, flooding and drainage influence redox chemistry and consequently trace metal solubility and thus uptake by rice plants. Current knowledge on how the dynamics in redox chemistry affect the solubility of trace metals in contaminated paddy soils is still limited. The objectives of our study were to investigate (i) the effects of flooding and drainage on trace metal solubility in paddy soils and (ii) to what extent a multi-surface modeling approach can predict trace metal solubility under changing redox conditions. We performed a column experiment with two contaminated paddy soils with similar soil properties but contrasting pH. During two successive flooding and drainage cycles, dynamics in Eh, pH and dissolved organic matter concentrations greatly affected trace metal solubility for both soils. Multi-surface model predictions indicate that under aerobic conditions, the higher pH of the alkaline soil leads to a stronger complexation of trace metals by reactive surfaces of the soil and, consequently, to lower dissolved concentrations than in the acidic soil. Under anaerobic conditions, predictions shows that sulfide precipitates control trace metal solubility in both soils, but still the higher pH of the alkaline soil leads to lower trace metal concentrations in soil solution at equilibrium. Furthermore, model calculations showed that stoichiometry and solubility of copper sulfide minerals can substantially affect solubility of other trace metals especially when trace element concentrations exceed soil sulfate concentrations. This stoichiometry and solubility should be considered when predicting the solubility of trace metals under anaerobic conditions.

The field Donnan Membrane Technique (DMT) has been used successfully to measure in-situ free trace metal concentrations in surface waters. However, it has not been applied previously in submerged soil systems including flooded paddy rice fields. We tested this technique in a column experiment with a flooded paddy soil contaminated with trace metals and compared the DMT measurements with predictions from a geochemical speciation model. Flooding led to a strong gradient in the redox potential (Eh) along the soil column, and the pH and concentrations of Mn, Fe, and dissolved organic carbon increased with decreasing Eh. Total dissolved trace metal concentrations decreased from the overlying water layer to the soil layers, which might be ascribed to the elevated pH outweighing the effect of the increased DOC concentrations under anaerobic conditions. Also, free trace metal concentrations were lower in the soil solution of the upper and bottom soil layers than in the overlying water layer, largely due to the increased pH under anaerobic conditions. The DMT measurements and model predictions were similar in the aerobic water layer, except for Pb. In both anaerobic soil layers, however, Cu and Pb were poorly predicted. The applied geochemical modeling approach, which is frequently being used and performs well under aerobic conditions, does not fully capture all the chemical processes occurring under anaerobic conditions. Overall, the field DMT proved to be a useful tool for the in-situ measurement of free trace metal concentrations in flooded paddy soils.

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.

In het kader van de nationale en internationale verplichting om de emissies en belasting van oppervlaktewater te rapporteren, is de uit- en afspoeling van nutrienten en zware metalen uit het landelijk gebied berekend. Met het landelijke emissiemodel STONE en STONE-ZM zijn de emissies naar het oppervlaktewater doorgerekend. Voor het bepalen van een gemiddelde verwachting van de uit- en afspoeling is de klimaatreeksmethode toegepast om de grote effecten van de dynamiek in het weer te filteren. Aangezien het neerslagoverschot van grote invloed is op de uit- en afspoeling van stikstof en fosfor.

The 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.

Climate change is projected to significantly affect the concentrations and mobility of contaminants, such as metals and pathogens, in soil, groundwater and surface water. Climate- and land management-induced changes in soil organic carbon and dissolved organic carbon levels may promote the transport of toxic substances, such as copper and cadmium, and pathogenic microorganisms, ultimately affecting the exposure of humans and ecosystems to these contaminants. In this study, we adopted the Century model to simulate past (1900 - 2010), present, and future (2010 - 2100) SOC and DOC levels for a sandy and a loamy soil typical for Central and Western European conditions under three land use types (forest, grassland and arable land) and several future scenarios addressing climate change and land management change. The climate scenarios were based on the KNMI'06 G+ and W+ scenarios from the Royal Dutch Meteorological Institute. The simulated current SOC levels were compared to observed SOC values derived from various Dutch soil databases, taking into account the different soil depths the simulated and observed values refer to. The simulated SOC levels were generally in line with the observed values for the different kinds of soil and land use types. Climate change scenarios resulted in a decrease in both SOC and DOC for the grassland systems, whereas in the arable land (on sandy soil) and in the forest systems, SOC was found to increase and DOC to decrease. A sensitivity analysis of the individual effects of changes in temperature and precipitation showed that the effect of temperature predominates over the effect of precipitation. A reduction in the application rates of artificial fertilizers leads to a decrease in the SOC stocks and the leached carbon rates in the arable land systems, but has a negligible effect on SOC and DOC levels of the grassland systems. This study demonstrated the ability of the Century model to simulate climate change and agricultural management effects on SOC dynamics. The following step of this study will involve the translation of the soil organic matter pools as simulated with Century model, into pools of different metal binding capacity to be used for the metal partitioning and leaching modelling.

In het kader van de nationale en internationale verplichting om de emissies en belasting van oppervlaktewater te rapporteren is de uit- en afspoeling van nutrienten en zware metalen uit het landelijk gebied berekend. Met het landelijke emissiemodel STONE en STONE-ZM zijn de emissies naar het oppervlaktewater doorgerekend. Voor de consistentie is hetzelfde model gebruikt dat ook gebruikt is voor de Evaluatie Meststoffenwet 2012. Voor het bepalen van een gemiddelde verwachting van de uit- en afspoeling is een nieuwe methode toegepast om de grote effecten van de dynamiek in het weer te filteren.

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.

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.