J.E. Groenenberg

Impact of soil properties on critical concentrations of cadmium, lead, copper, zinc, and mercury in soil and soil solution in view of ecotoxicological effects

Risk assessment for metals in terrestrial ecosystems, including assessments of critical loads, requires appropriate critical limits for metal concentrations in soil and soil solution. This chapter presents an overview of methodologies used to derive critical (i) reactive and total metal concentrations in soils and (ii) free metal ion and total metal concentrations in soil solution for Cd, Pb, Cu, Zn, and Hg, taking into account the effect of soil properties related to ecotoxicological effects. Most emphasis is given to the derivation of critical free and total metal concentrations in soil solution, using available NOEC soil data and transfer functions relating solid-phase and dissolved metal concentrations. This approach is based on the assumption that impacts on test organisms (plants, microorganisms, and soil invertebrates) are mainly related to the soil solution concentration (activity) and not to the soil solid-phase content. Critical Cd, Pb, Cu, Zn, and Hg concentrations in soil solution vary with pH and DOC level. The results obtained are generally comparable to those derived for surface waters based on impacts to aquatic organisms. Critical soil metal concentrations, related to the derived soil solution limits, can be described as a function of pH and organic matter and clay content, and varying about one order of magnitude between different soil types.

Uncertainty Analysis of the Nonideal Competitive Adsorption−Donnan Model: Effects of Dissolved Organic Matter Variability on Predicted Metal Speciation in Soil Solution

Ion binding models such as the nonideal competitive adsorption-Donnan model (NICA-Donnan) and model VI successfully describe laboratory data of proton and metal binding to purified humic substances (HS). In this study model performance was tested in more complex natural systems. The speciation predicted with the NICA-Donnan model and the associated uncertainty were compared with independent measurements in soil solution extracts, including the free metal ion activity and fulvic (FA) and humic acid (HA) fractions of dissolved organic matter (DOM). Potentially important sources of uncertainty are the DOM composition and the variation in binding properties of HS. HS fractions of DOM in soil solution extracts varied between 14 and 63% and consisted mainly of FA. Moreover, binding parameters optimized for individual FA samples show substantial variation. Monte Carlo simulations show that uncertainties in predicted metal speciation, for metals with a high affinity for FA (Cu, Pb), are largely due to the natural variation in binding properties (i.e., the affinity) of FA. Predictions for metals with a lower affinity (Cd) are more prone to uncertainties in the fraction FA in DOM and the maximum site density (i.e., the capacity) of the FA. Based on these findings, suggestions are provided to reduce uncertainties in model predictions.

Use of reactive materials to bind phosphorus

Phosphorus (P) losses from agricultural soils have caused surface water quality impairment in many regions of the world, including The Netherlands. Due to the large amounts of P accumulated in Dutch soils, the generic fertilizer and manure policy will not be sufficient to reach in time the surface water quality standards of the European Water Framework Directive. Additional measures must be considered to further reduce P enrichment of surface waters. One option is to immobilize P in soils or manure or to trap P when it moves through the landscape by using reactive materials with a large capacity to retain P. We characterized and tested two byproducts of the process of purification of deep groundwater for drinking water that could be used as reactive materials: iron sludge and iron-coated sand. Both materials contain low amounts of inorganic contaminants, which also have a low (bio)availability, and bound a large amount of P. We could describe sorption of P to the iron sludge in batch experiments well with the kinetic Freundlich equation (Q = × t (m) × C(n)). Kinetics had a large influence on P sorption in batch and column experiments and should be taken into account when iron-containing materials are tested for their capability to immobilize or trap P. A negative aspect of the iron sludge is its low hydraulic conductivity; even when mixed with pure sand to a mixture containing 20% sludge, the conductivity was very low, and only 10% sludge may be needed before application is possible in filters or barriers for removing P from groundwater. Due to its much higher hydraulic conductivity, iron-coated sand has greater potential for use under field conditions. Immobilizing P could be an option for using iron sludge as a reactive material.

The use of assemblage models to describe trace element partitioning, speciation, and fate: a review.

The fate of trace elements in soils, sediments, and surface waters is largely determined by their binding to reactive components, of which organic matter, metal oxides, and clays are considered most important. Assemblage models, combining separate mechanistic complexation models for each of the reactive components, can be used to predict the solid-solution partitioning and speciation of trace elements in natural environments. In the present review, the authors provide a short overview of advanced ion-binding models for organic matter and oxides and of their application to artificial and natural assemblages. Modeling of artificial assemblages of mineral components and organic matter indicates that the interactions between organic and mineral components are important for trace element binding, particularly for oxyanions. The modeling of solid-solution partitioning in natural systems is generally adequate for metal cations but less so for oxyanions, probably because of the neglect of organic matter-oxide interactions in most assemblage models. The characterization of natural assemblages in terms of their components (active organic matter, reactive oxide surface) is key to successful model applications. Improved methods for characterization of reactive components in situ will enhance the applicability of assemblage models. Collection of compositional data for soil and water archetypes, or the development of relationships to estimate compositions from geospatially available data, will further facilitate assemblage model use for predictive purposes.

Evaluation of an approach for the characterization of reactive and available pools of 20 potentially toxic elements in soils: Part II – Solid-solution partition relationships and ion activity in soil solutions

To assess environmental risks related to contaminants in soil it is essential to predict the available pool of inorganic contaminants at regional scales, accounting for differences between soils from variable geologic and climatic origins. An approach composed of a well-accepted soil extraction procedure (0.01 M CaCl(2)) and empirical Freundlich-type models in combination with mechanistically based models which to date have been used only in temperate regions was applied to 136 soils from a South European area and evaluated for its possible general use in risk assessment. Empirical models based on reactive element pools and soil properties (pH, organic carbon, clay, total Al, Fe and Mn) provided good estimations of available concentrations for a broad range of contaminants including As, Ba, Cd, Co, Cu, Hg, Mo, Ni, Pb, Sb, Se and Zn (r(2): 0.46-0.89). The variation of the pools of total Al in soils expressed the sorptive capacity of aluminosilicates and Al oxides at the surfaces and edges of clay minerals better than the actual variability of clay contents. The approach has led to recommendations for further research with particular emphasis on the impact of clay on the solubility of As and Sb, on the mechanisms controlling Cr and U availability and on differences in binding properties of soil organic matter from different climatic regions. This study showed that such approach may be included with a good degree of certainty for first step risk assessment procedures to identify potential risk areas for leaching and uptake of inorganic contaminants in different environmental settings.

Evaluation of approaches to calculate critical metal loads for forest ecosystems.

This paper evaluates approaches to calculate acceptable loads for metal deposition to forest ecosystems, distinguishing between critical loads, stand-still loads and target loads. We also evaluated the influence of including the biochemical metal cycle on the calculated loads. Differences are illustrated by examples of Cd, Cu, Pb and Zn for a deciduous forest on five major soil types in the Netherlands. Stand-still loads are generally lower than critical loads, which in turn are lower than the target loads indicating that present levels are below critical levels. Uncertainties in the calculated critical loads are mainly determined by the uncertainty in the critical limits and the chemical speciation model. Including the metal cycle has a small effect on the calculated critical loads. Results are discussed in view of the applicability of the critical load concept for metals in future protocols on the reduction in metal emissions.

Reducing phosphorus loading of surface water using iron-coated sand.

Phosphorus losses from agricultural soils is an important source of P in surface waters leading to surface water quality impairment. In addition to reducing P inputs, mitigation measures are needed to reduce P enrichment of surface waters. Because drainage of agricultural land by pipe drainage is an important pathway of P to surface waters, removing P from drainage water has a large potential to reduce P losses. In a field trial, we tested the performance of a pipe drain enveloped with Fe-coated sand, a side product of the drinking water industry with a high ability to bind P, to remove P from the drainage water. The results of this trial, encompassing more than one hydrological season, are very encouraging because the efficiency of this mitigation measure to remove P amounted to 94%. During the trial, the pipe drains were below the groundwater level for a prolonged time. Nevertheless, no reduction of Fe(III) in the Fe-coated sand occurred, which was most likely prevented by reduction of Mn oxides present in this material. The enveloped pipe drain was estimated to be able to lower the P concentration in the effluent to the desired water quality criterion for about 14 yr. Manganese oxides are expected to be depleted after 5 to 10 yr. The performance of the enveloped pipe drain, both in terms of its ability to remove P to a sufficiently low level and the stability of the Fe-coated sand under submerged conditions in the long term, needs prolonged experimental research.

Evaluation of the Single Dilute (0.43 M) Nitric Acid Extraction to Determine Geochemically Reactive Elements in Soil

Recently a dilute nitric acid extraction (0.43 M) was adopted by ISO (ISO-17586:2016) as standard for extraction of geochemically reactive elements in soil and soil like materials. Here we evaluate the performance of this extraction for a wide range of elements by mechanistic geochemical modeling. Model predictions indicate that the extraction recovers the reactive concentration quantitatively (>90%). However, at low ratios of element to reactive surfaces the extraction underestimates reactive Cu, Cr, As, and Mo, that is, elements with a particularly high affinity for organic matter or oxides. The 0.43 M HNO3 together with more dilute and concentrated acid extractions were evaluated by comparing model-predicted and measured dissolved concentrations in CaCl2 soil extracts, using the different extractions as alternative model-input. Mean errors of the predictions based on 0.43 M HNO3 are generally within a factor three, while Mo is underestimated and Co, Ni and Zn in soils with pH > 6 are overestimated, for which possible causes are discussed. Model predictions using 0.43 M HNO3 are superior to those using 0.1 M HNO3 or Aqua Regia that under- and overestimate the reactive element contents, respectively. Low concentrations of oxyanions in our data set and structural underestimation of their reactive concentrations warrant further investigation.

The Impact of Atmospheric Deposition of Non-Acidifying Substances on the Quality of European Forest Soils and the North Sea

In the pilot study ESQUAD the impact of atmospheric deposition of three heavy metals (cadmium, copper and lead) and two persistent organic pollutants (benzo(a)-pyrene and lindane) on the quality of European soils and seawater has been calculated. Calculations have been made of atmospheric transport and deposition using a detailed emissions database for Europe. This enabled deposition maps to be produced to a resolution of approximately 50 km. The distribution of pollutant concentrations in forest soils was calculated for each grid cell using a database of soil property parameters in Europe. For the North Sea, a model was used to map long-term concentrations in water and sediment, which are due to atmospheric deposition and other, non-atmospheric sources. The model calculations allowed detailed comparisons of deposition fluxes and concentrations of the substances studied with critical loads and environmental quality threshold values, including critical loads. Although significant uncertainties were identified, the study gives insight in how threshold exceedance rates in Europe relate to pollutant type, threshold type, environmental compartment and chemophysical phase (adsorbed, dissolved). For all pollutants and for all compartments exceedances were calculated for at least some of the quality thresholds that were chosen.

The use of upscaling procedures in the application of soil acidification models at different spatial scales

Different soil acidification models have been developed for use on different scales, i.e. NUCSAM for the local scale, RESAM for the regional (national) scale and SMART for the continental scale. This paper focuses on the uncertainties associated with scale transfer by a simpler model description by (i) temporal aggregation of process descriptions, (ii) neglection of processes associated with vertical aggregation of soil layers and (iii) the use of less detailed formulations of processes (process aggregation) and by spatial aggregation of input data. Results obtained for simulations in acid (sandy) soils indicate that (i) temporal aggregation and process aggregation have a limited impact on the long-term (decades) annual response of soil solution chemistry to atmospheric deposition, (ii) vertical aggregation mainly affects predictions of solutes which show a strong concentration gradient with depth and (iii) spatial aggregation hardly affects the average output for a given forest/soil combination. However, ignoring the variability in input parameters, largely affects the frequency distribution of model outputs in a region. Results imply that model simplification is an adequate step in the upscaling of modelling results from a local to a regional scale.