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Being able to predict the behavior of trace elements in the environment is crucial for environmental risk assessment studies. For this reason, modeling, in addition to experimental methods, has become an indispensable tool to better understand the (bio)-geochemistry of trace elements and the processes involved in their availability, transport and ecotoxicity. In this chapter we briefly outline the development of geochemical modeling over time and its basic principles. A comprehensive description of the state-of-the-art ion-binding and surface complexation models presently available for dissolved and particulate organic matter, metal (hydr)oxides of aluminum, iron, manganese and silica and clay minerals is given. A significant part of this chapter is dedicated to the application of these models for studying surface waters and soils. The most common model platforms used for this purpose together with the available (thermodynamic) databases of model parameters are summarized. In two separate sections we highlight the application of an assemblage model (with submodels for the various adsorbents) to describe trace element solid-solution partitioning and speciation in surface waters and soils; here particular attention is given to the derivation of site-specific inputs concerning the geochemical reactive metal content and the contents of adsorbents metal (hydr)oxides, clay and organic matter). Consideration is therefore given to the most recent developments in bio-geochemical modeling to link metal speciation to bioavailability, biotic accumulation and toxicity. Finally, future prospects of geochemical modeling are discussed, giving an overview of the potential directions for development.

Being able to predict the behavior of trace elements in the environment is crucial for environmental risk assessment studies. For this reason, modeling, in addition to experimental methods, has become an indispensable tool to better understand the (bio)-geochemistry of trace elements and the processes involved in their availability, transport and ecotoxicity. In this chapter we briefly outline the development of geochemical modeling over time and its basic principles. A comprehensive description of the state-of-the-art ion-binding and surface complexation models presently available for dissolved and particulate organic matter, metal (hydr)oxides of aluminum, iron, manganese and silica and clay minerals is given. A significant part of this chapter is dedicated to the application of these models for studying surface waters and soils. The most common model platforms used for this purpose together with the available (thermodynamic) databases of model parameters are summarized. In two separate sections we highlight the application of an assemblage model (with submodels for the various adsorbents) to describe trace element solid-solution partitioning and speciation in surface waters and soils; here particular attention is given to the derivation of site-specific inputs concerning the geochemical reactive metal content and the contents of adsorbents metal (hydr)oxides, clay and organic matter). Consideration is therefore given to the most recent developments in bio-geochemical modeling to link metal speciation to bioavailability, biotic accumulation and toxicity. Finally, future prospects of geochemical modeling are discussed, giving an overview of the potential directions for development.

Arkhipova et al. caution that the limitations of structural models be taken into account when interpreting crystallographic data., Crystal structures provide visual models of biological macromolecules, which are widely used to interpret data from functional studies and generate new mechanistic hypotheses. Because the quality of the collected x-ray diffraction data directly affects the reliability of the structural model, it is essential that the limitations of the models are carefully taken into account when making interpretations. Here we use the available crystal structures of members of the glutamate transporter family to illustrate the importance of inspecting the data that underlie the structural models. Crystal structures of glutamate transporters in multiple different conformations have been solved, but most structures were determined at relatively low resolution, with deposited models based on crystallographic data of moderate quality. We use these examples to demonstrate the extent to which mechanistic interpretations can be made safely.

Environmental contextStudying the mechanism of binding between metals and natural organic matter is fundamental to understanding the transport and availability of these contaminants in the environment. The influence of sample treatment on the purification of organic matter showed significant differences in the interaction with metals. The results will contribute to improved modelling of metal binding to organic matter in soils, thereby providing a basis for a more realistic risk assessment. AbstractWe studied the changes in metal binding characteristics of extracted humic acids induced by HF/HCl treatment followed by dialysis, i.e. the last step of the International Humic Substances Society (IHSS) extraction protocol. We performed metal binding experiments with both the alkaline-extracted material (AE) and the fully purified (FP) humic acid using the electrochemical stripping technique (AGNES) and modelled the results using the NICA-Donnan model. The results showed an increase of free Zn, Cd and Pb concentrations of similar to 1 order of magnitude for the AE compared with the FP. These differences may be mostly explained by the different carbon content (51.3% FP and 36.5% AE) associated with an AE/FP carboxyl ratio of 0.5. Simulations using the NICA-Donnan model showed that halving the amount of carboxylic groups (Q(max,1)) for the FP reduced this difference to 0.25 log units for Cd and Zn and to 0.15 log unit for Pb. There is a clear need for further research on the differences between purified v. less-disturbed natural organic material, which will contribute to improved modelling of metal binding to organic matter in soils, hence providing a basis for a more realistic risk assessment. Coordenadoria de Aperfeicoamento do Pessoal de Nivel Superior (CAPES CSF) [981313-6] Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq PVE) [400572/2013-3] French national research agency (ANR) [ANR-10-LABX-21-01/LABEX RESSOURCES 21] Portuguese national funding agency for science, research and technology [FCT-ANR/AAG-MAA/0065/2012] Region Lorraine

The solubility of silver(I) in many soils is controlled by complexation reactions with organic matter. In this work we have compared the ability of isolated humic and fulvic acids to bind silver(I) with that of mor and peat materials. One new data set for Suwannee River Fulvic Acid was produced, which was consistent with published data sets for isolated fulvic and humic acids. The ability of soil materials to bind silver(I) was studied as a function of pH in the range 2.5-5.0, at a wide range of silver(I)-to-soil ratios (10(-4.2) - 10(-1.9) mol kg(-1)). By calibrating the Stockholm Humic Model on the humic and fulvic acids data sets, we showed that binding of silver(I) to both types of soil materials was much stronger (up to 2 orders of magnitude) than predicted from the silver(I) binding properties of the isolated humic materials. Thus, the approach taken for many other metals, that is, to model solubility in soils by using metal and proton binding parameters derived from isolated humic and fulvic acids, cannot be used for silver(I). One possible explanation for the discrepancy could be that silver(I) predominately interacted with various biomolecules in the soil samples, instead of humic- and fulvic-acid type materials. QC 20160913

The anionic charge of humic substances (HS) plays a major role in the interaction of HS with other components. Therefore, the potential of the polyelectrolyte titration technique to obtain the charge density of HS in simple 1–1 electrolyte solutions has been investigated. Titrations are carried out with an automatic titrator combined with the “Mutek particle charge detector” which allows determination of the Mutek potential and the pH as a function of the added amount of titrant which is a solution of poly-diallyldimethylammonium chloride (polyDADMAC), a cationic strong polyelectrolyte. When the Mutek potential reverses its sign the iso-electric point (IEP) of the polyDADMAC–HS complex is reached. The polyDADMAC/HS mass ratio at the IEP gives information on the HS charge density and from the pH changes in solution an estimate of the charge regulation in the HS–polyDADMAC complex can be obtained. In general, for polyDADMAC–HS complexes an increase in the dissociation of the acid groups of HS is found (charge regulation). The charge regulation decreases with increasing concentration of 1–1 background electrolyte. Cation incorporation can be neglected at 1–1 electrolyte concentrations ⩽ 1 mmol L−1 and a 1–1 stoichiometry exists between the polyDADMAC and HS charge. However, at these low salt concentrations the charge regulation is substantial. A detailed analysis of purified Aldrich humic acid (PAHA) at pH 5 and a range of KCl concentrations reveals that the anionic charge of PAHA in the complex increases at 5 mmol L−1 KCl by 30% and at 150 mmol L−1 KCl by 12%. On the other hand, increasing amounts of K+ become incorporated in the complex: at 5 mmol L−1 KCl 5% and at 150 mmol L−1 KCl 24% of the PAHA charge is balanced by K+. By comparing at pH 5 the mass ratios polyDADMAC/PAHA in the complex at the IEP with the theoretical mass ratios of polyDADMAC/PAHA required to neutralize PAHA in the absence of charge regulation and K+ incorporation, it is found that at 50 mmol L−1 KCl the extra negative charge due to the interaction between polyDADMAC and PAHA is just compensated by K+ incorporation in the complex. Therefore, a pseudo 1–1 stoichiometry exists at about 50 mmol L−1 1–1 electrolyte concentration and only at this salt concentration polyDADMAC titrations and conventional proton titrations give identical results. Most likely this is also true for other HA samples and other pH values. For FA further study is required to reveal the conditions for which polyDADMAC and proton titrations give identical results.

The charge of poly(acrylic acid) (PAA) in dilute aqueous solutions depends on pH and ionic strength. We report new experimental data and test various models to describe the deprotonation of PAA in three different NaCl concentrations. A simple surface complexation approach is found to be very successful: the constant capacitance model requires one pKa value and one capacitance for excellent fits to the data, with both parameters depending on ionic strength. The use of a self-consistent set of diffuse double layer parameters with one pKa for flat, spherical, and cylindrical geometry does not result in a satisfactory description of the data, and a number of adjustments to that model were tested to improve the fit. The basic Stern model (BSM) was tested with both plate and cylinder geometry. The cylinder geometry along with strong electrolyte binding was found to be superior to a similar approach involving weak electrolyte binding both in terms of goodness of fit and self-consistency of the parameters. The third approach, the non-ideal competitive consistent adsorption-Donnan (NICCA-Donnan) model, involving one functional group, allows an excellent description of the experimental data. Finally, the polyacid chain was modeled using a mechanistically more realistic self-consistent field (SCF) approach, which allows for radially inhomogeneous distributions of the charges and radial variations in the polymer density and electrostatic potential, while the functional groups can be in protonated, deprotonated, or complexed states. One functional group was insufficient for a satisfactory description of the data. With two segments (one monoprotic, the other diprotic) a reasonable description of the data, including the ionic strength dependence, is achieved, and the tendency of the size of the macro-ion with pH and ionic strength is as expected. This model has the fewest adjustable parameters and is considered the most realistic and comprehensive among the models tested

The transition from anaerobic to aerobic rice (Oryza sativa L.) cultivation has been reported to decrease Zn bioavailability. To determine and understand the differences in plant Zn uptake between anaerobic and aerobic rice cultivation systems, a field plot experiment was conducted with direct-seeded rice grown on a low-Zn soil under both anaerobic and aerobic conditions. Results showed that the mass fraction of Zn in shoots and Zn uptake of plants in the aerobic field was significantly lower than in the anaerobic field. Visual Zn deficiency symptoms as whitish-brown necrotic patches on leaves were more severe on plants grown in aerobic soils than plants in anaerobic soils, indicating reduced Zn bioavailability. To determine whether the underlying causes could be of a geochemical nature, a controlled soil incubation experiment was done. Using a fully parameterized model, we found that the difference in plant Zn uptake between the two cultivation systems was small compared with that predicted by geochemical modeling, assuming Zn uptake is controlled by the soluble fraction in the soil. Whereas individual effects of soil factors (e.g., pH) were demonstrated to cause large variations in Zn concentration, only about a 15% difference in plant Zn uptake was observed. This large discrepancy reveals that the consideration of separate soil chemical processes, instead of their integrated assessment, may be inappropriate. We speculated that the discrepancy could also be associated with the chemical conditions in the rhizosphere, where the local acidity, dissolved organic C, and redox conditions may deviate significantly from the bulk soil on which the geochemical analysis was based

The performance of a multisurface sorption model approach, composed of well-accepted surface complexation models in combination with published "generic" parameter sets, is evaluated for its possible use in risk assessment. For that purpose, the leaching of a broad range of potential soil contaminants (Ni, Cu, Zn, Cd, Pb, Ba, Cr, Co, Mo, V, Sn, Sb, S, As, Se) from eight diffusely and industrially contaminated soils is predicted simultaneously without any parameter optimization. The model approach includes aqueous speciation in combination with sorption to organic matter (NICA-Donnan model), Fe/Al(hydr)oxides (Generalized Two-Layer Model), and clay (Donnan model). Independent data generated by pH-static leaching experiments, performed with individual subsamples over a wide pH range (pH 0.4-12), provide a sensitive evaluation of the model performance. Root-mean-squared error values between predicted and measured log concentrations over the entire pH range, RMSE(log), are < 0.5 for Cu, Ni, Cd, Co, S, and Se, and RMSE(log) < 1 for Zn, Ba, Cr, Pb, Sn, Mo, Sn and As. The approach without parameter optimization has led to recommendations for further research with particular emphasis on identification of leaching mechanisms for Pb, Mo, Sb, and V and further expansion of the data sets to reduce the uncertainty of the available generic sorption parameters for Sn, Sb, Ba, Cr, and V.

Interactions of purified Aldrich humic acid (PAHA) with the protein lysozyme (LSZ) are studied with dynamic light scattering and isothermal titration calorimetry by mixing LSZ and PAHA at various mass ratios. In solution LSZ is positive and PAHA is negative at the investigated pH values. Up to moderate KCl concentrations no aggregation occurs for LSZ and for PAHA aggregated particles with an average radius of 80 nm are present Complexation of PAHA with LSZ starts as soon as PAHA is added to LSZ and is followed by aggregation when the isoelectric-point (IEP) of the complexes is approached. Aggregation is gradual for 50 mM KCl and sudden for low KCl concentrations. The aggregate size is at its maximum at the IEP of the complexes. At mass ratios beyond the IEP the aggregates partially disaggregate. Positively charged complexes of PAHA and LSZ, formed in the absence of salt, strongly aggregate upon salt addition. Mixing of LSZ and PAHA is initially enthalpically driven. Near the IEP complexation and aggregation are due to hydrophobic forces (structural reorganization) and counterion release. The observations are relevant for other HA-protein systems when the protein is positively charged.

Four soils were collected from different sites of China in Lechang (LC, Guangdong province), Changsha (CS, Hunan province), Jiaxing UX, Zhejiang province) and Hangzhou (HZ, Zhejiang province), and were spiked with Cu (50 mg kg(-1)) and Cd (5 mg kg(-1)). The effects of rice straw addition (6%) on the chemical distribution of both metal ions were studied by measuring the soluble metal ion concentrations and the free metal ion concentrations (using the Donnan membrane technique) after 1-, 3- and 6-month incubation. Results show that the addition of rice straw increased soil pH by about 0.4 pH unit on average, and increased DOC significantly in soil LC, CS and JX, but not in soil HZ. With the addition of rice straw, total soluble Cu concentration increased from 0.82 mu mol l(-1) (0.26-2.4 mu mol l(-1)) to 1.22 mu mol l(-1) (0.70-3.60 mu mol l(-1)), whereas total soluble Cd concentration decreased from 20 nmol l(-1) (2-70 nmol l(-1)) to 15 nmol l(-1) (2-56 nmol l(-1)). When rice straw was added, both free Cu 2 and Cd 21 concentrations decreased, for free Cu2+ concentration from 217 nmol l(-1) (31 to 369 nmol l(-1)) to 124 nmol l(-1) (22 to 263 nmol l(-1)) and for free Cd2+ concentration from 16 nmol l(-1) (1-55 nmol l(-1)) to 12 nmol l(-1) (1-43 nmol l(-1)). With the increase of incubation time, free Cu2+ concentration tended to increase but free Cd2+ concentration decreased. Speciation model calculations show that compared to the binding capacity of soil organic matter, the capacity of rice straw is much less important. The decrease of free metal ion concentration upon rice straw addition can be attributed mainly to the increased pH. The higher DOC content in the rice straw treatment could be the reason for higher soluble Cu concentration when rice straw was added. Adsorption to DOC is much less important for Cd than for Cu. Calculation also shows that adsorption to clay minerals plays a more important role for Cd than for Cu, which may explain the stronger ageing effects on Cd distribution. (c) 2008 Elsevier B.V. All rights reserved.

There is growing concern about the accumulation of metals in tropical agricultural soils. In this study, experimental results from batch studies were used to test whether multi-surface geochemical models could describe metal binding in selected Vietnamese soils. The multi-surface models considered metal binding to iron hydroxides (using the diffuse layer model), organic matter (Stockholm Humic model and NICA-Donnan model), and phyllosilicate clay (Gaines-Thomas equation) as well as complexation to dissolved organic and inorganic ligands in the solution phase. We found that for total dissolved Cd, Cu and Zn the two multi-surface models being tested provided very good model fits for all soils, as evidenced by low root-mean square errors between model predictions and observations. These results suggest that organic matter is an important sorbent for many metals in these soils. However, poor fits were obtained for Cr(III), Mn and Pb for all soils. The study also suggests that the pH is the main factor that controls the solubility of metals in tropical Fluvisols and Acrisols subjected to application of biosolids and wastewater, and that advanced multi-surface models can be used to simulate the binding and release of many trace metals. QC 20100525

Adsorption of randomly branched polyelectrolytes, "hairy" particles and internally structured macromolecules, collectively denoted as heterogeneously charged nanoparticles, on charged surfaces is important in many technological and natural processes. In this paper, we will focus on (1) the charge regulation of both the nanoparticle and the surface and (2) the surface complexation between the particle functional groups and the surface sites and will theoretically study the adsorption using the extended surface complexation approach. The model explicitly considers the electrochemical potential of a nanoparticle with an average (smeared-out) structure and charge both in bulk solution and on the surface to obtain the equilibrium adsorption. The chemical heterogeneity of the particle is described by a distribution of the protonation constant. Detailed analysis of the chemical potential of the adsorbed nanoparticle reveals that the pH and salt dependence of the adsorption can be largely explained by the balance between an energy gain resulting from the particle and surface charge regulation and the surface complexation and an energy loss from the unfavorable interparticle electrostatic repulsion close to the surface. This conclusion is also supported by the strong impacts that the chemical heterogeneity of the particle functional groups, the magnitude of the surface complexation, the number of the functional groups, and the size of the particle have on the adsorption.

The development of speciation and surface complexation models to calculate partitioning of metals between the soil solid phase and soil solution has made a large progress. We evaluated the use and practical applicability of an assemblage of complexation models to predict sorption of Cd, Cu, Ni, Pb and Zn. We used 353 samples which cover a wide range of soil properties and metal contents. For sorption of cations to solid and dissolved organic matter the NICA-Donnan model was used, to clay minerals a non-specific Donnan type exchange model, and to metal(hydr)oxides a two-site DDL model. Calculated solution concentrations agree well with measurements, except for Pb where calculations overestimate concentrations by one order of magnitude on average. Some highly Zn contaminated samples show relatively large deviations between measured and calculated concentrations. This is most likely caused by Zn containing minerals which are included in the total amount of reactive metals in the soil as determined by acid extraction. Hence, such models can be used for practical applications if one is aware of the possible complications. When the “total reactive metal content” includes a substantial amount of precipitated metals, which may occur for heavily contaminated soils, the model tends to overestimate concentrations in solution.

Dissolved organic carbon (DOC) is a key component involved in metal displacement in soils. In this study, we investigated the concentration profiles of soil-borne DOC, Cu and Zn at various irrigation rates with synthetic rain water under quasi steady-state conditions, using repacked soil columns with a metal-polluted topsoil and two unpolluted subsoils. Soil solution was collected using suction cups installed at centimeter intervals over depth. In the topsoil the concentrations of DOC, dissolved metals (Zn and Cu), major cations (Ca2+ and Mg2+) and anions ( and ) increased with depth. In the subsoil, the Cu and Zn concentrations dropped to background levels within 2 cm. All compounds were much faster mobilized in the first 4 cm than in the rest of the topsoil. DOC and Cu concentrations were higher at higher flow rates for a given depth, whereas the concentrations of the other ions decreased with increasing flow rate. The decomposition of soil organic matter resulted in the formation of DOC, , and and was the main driver of the system. Regression analysis indicated that Cu mobilization was governed by DOC, whereas Zn mobilization was primarily determined by Ca and to a lesser extent by DOC. Labile Zn and Cu2+ concentrations were well predicted by the NICA-Donnan model. The results highlight the value of high-resolution in-situ measurements of DOC and metal mobilization in soil profiles.

International audience; The exchange kinetics of Cd, Cu, Pb, and Zn in seven mining and smelting-contaminated soils and the other two anthropogenically contaminated soils was investigated by using multi-elementary stable isotopic exchange kinetic (SIEK) method, and the experimental results were successfully interpreted by modelling using a sum of pseudo first order kinetics equations. SIEK results show that in the studied soils the isotopic exchange of Cd is a relatively fast process, and the exchange almost reaches an apparent plateau after 3-d equilibration; whereas for Cu, Pb, and Zn, the exchange is more sluggish, suggesting that it is important to understand the time-dependent metal mobility for risk assessment and management of contaminated soils. In most of the soils, the total isotopically exchangeable pool is divided, for all the metals, into two distinct pools: a fast exchangeable pool (E-1) with a kinetic rate constant k(1) having values around 1 min(-1) and a much slower exchangeable pool (E-2) with k(2) ranging from 0.0001 min(-1) to 0.001 min(-1). The distribution of the two exchangeable pools varies significantly among metals. The amount of isotopically exchangeable Cd related to the fast pool is dominant, accounting for on average 60% of total isotopically exchangeable pool in the soils; whereas this pool is smaller for Cu, Zn, and Pb. The sequence of average k(1) values is Cd > Pb approximate to Zn > Cu, consistent with the reported sequence of stability constants of metal-humic substances (HS) complexes while the average k(2) values follow the order: Cd > Pb > Cu > Zn, probably controlled by the slow desorption of metal ions associated with soil organic matter (SOM) fraction. Our results imply that further study on the exchange kinetics of metals on each individual sorption surface in soils, especially SOM, is critical to help understanding the overall exchange kinetics of heavy metals in whole soils

The adsorption of humic acids (HA) to goethite (at pH 3-11) and the proton co-adsorption (at pH 4.0, 5.5, and 7.0) were measured, and the results were compared to those of fulvic acids (FA). Compared to FA, the adsorption of HA is stronger and more ionic strength dependent. The adsorption of both HA and FA decreases with increasing pH. The relative change of the adsorption with pH is bigger for HA than for FA at relatively low pH. At relatively high pH, it is the opposite. Protons are released at pH 4.0 and co-adsorbed at pH 5.5 and 7.0 upon the adsorption of both HA and FA. The observed pH dependency of HA and FA adsorption is in agreement with the proton co-adsorption data. Model calculations show that the adsorbed FA particles are on average located in the Stern layer, whereas the adsorbed HA particles protrude beyond the Stern layer. The closer location to the surface of the adsorbed FA leads to stronger electrostatic interactions between the FA particles and the surface, which explains the larger amount of protons released at low pH and co-adsorbed at high pH with each mass unit of FA adsorbed than that with HA adsorbed. The model also reveals that for FA a mean-field (smeared-out) approximation is reasonable, but for HA a patchwise approach is more appropriate at relatively low loading.

In this paper, we characterize the leaching of heavy metals (Ni, Cu, Zn, Cd, and Pb) from eight contaminated soils over a wide range of pH (pH 0.4-12) using an original approach based on batch pH-static leaching experiments in combination with selective chemical extractions and geochemical modeling. The leached concentrations of the heavy metals are generally much lower than the total concentrations and show a strong pH dependency, resulting in "V-shaped" leaching curves with orders of magnitude changes in solution concentrations. The "multisurface" model used incorporates adsorption to dissolved and solid organic matter (NICA-Donnan), iron/aluminum (hydr)oxide (generalized two-layer model) and clay (Donnan model). These models were applied without modifications, and only the standard set of binding constants and parameters was used (i.e., without any fitting). The model predictions of heavy metal leaching are generally adequate and sometimes excellent. Results from speciation calculations are consistent with the well-recognized importance of organic matter as the dominant reactive solid phase in soils. The observed differences between soils with respect to element speciation in the solid phase correspond to the relative amounts of the reactive surfaces present in the soils. In the solution phase, complexes with dissolved organic matter (DOM) are predominant over most of the pH range. Free metal ions (Me2+) are generally the dominant species below pH 4. The combination of the experimental and modeling approach as used in this study is shown to be promising because it leads to a more fundamental understanding of the pH-dependent leaching processes in soils. The "multisurface" modeling approach, with the selected sorption models, is shown to be able to adequately predict the leaching of heavy metals from contaminated soils over a wide range of conditions, without any fitting of parameters.

Acidity (pH) has been realized to be the most important soil characteristic that modulates bioavailability of heavy metals by affecting both the chemical speciation of metals in soil and the metal binding to the active sites on biota. In this work, we show that besides soil pH, metal bioavailability also depends to a certain extent on the type of soil. A better understanding of the role of soil type in regulating metal availability can be achieved with the analysis of soil composition and with calculations using chemical speciation models. Results of pot experiments, in which three different soils were spiked with nickel, show that the EC50 of total nickel in decreasing the biomass production of oats varies widely (0.7-22.5 mmol kg(-1) soil, more than 30 times). pH (4.7-7.0) is the most important factor, explaining up to a factor of 14 difference of nickel bioavailability in the soils. The remaining variation is caused by other differences in soil composition (soil type). The bioavailability and toxicity of nickel in the organic matter-rich soil studied is less than half of that in the sandy and clay soil studied at a similar pH. The chemical calculations using a multi-surface speciation model show that soil organic matter binds Ni much stronger than clay silicates and iron (hydr)oxides within the acidic pH range, which supports the experimental findings. In all three soils, the EC50 of Ni expressed in terms of Ni in 0.01 M CaCl2 soil extraction is rather stable (24-58 microM), suggesting the possibility to use this extraction as an estimation of metal availability in soil.

Stripping chronopotentiometry at scanned deposition potential (SSCP) allows chemical heterogeneity in metal speciation to be unambiguously identified. In the labile regime, use of the Freundlich binding isotherm allows straightforward determination of parameters to describe the apparent stability and heterogeneity of metal complexes with humic substances. The extent of heterogeneity of metal binding by several humic substances follows the order Cu(ii) >> Pb(ii) > Cd(ii). The lability of metal complexes decreases from the foot to the top of the wave, and the greater the degree of heterogeneity, the more readily lability is lost. In the kinetic current regime, the Koutecký–Koryta approximation allows an expression to be obtained for the SSCP wave that provides a good estimate of the experimental data for metal complexes with moderate degrees of heterogeneity.