E.J.J. Kalis

Effects of humic acid and competing cations on metal uptake by Lolium perenne

Within the biotic ligand model, which describes relationships between chemical speciation and metal binding at an organisms surface, multicomponent (long-term) metal uptake by plants has seldom been studied. In the present work, we exposed perennial ryegrass to nutrient solutions with two levels of Cd, Cu, Ni, Pb, and Zn (1 and 0.1 microM) and with or without 30 mg/L of humic acid. Iron and Mn concentrations were constant over all treatments. The hypothesis tested was that humic acid lowers the free and labile metal concentration and, therefore, reduces the metal uptake and, finally, the metal content of the plant. The free metal ion concentrations in the nutrient solutions were measured by the Donnan membrane technique and labile metal concentrations by diffusive gradients in thin-films. The metal content of the shoots depends on the metal content of the roots. The metal content of the roots is a function of the adsorption of metals on the root surface. In a multicomponent system at metal concentrations of 1 microM, humic acid decreased Cu, Pb, and Fe adsorption at the root surface, but it increased Cd, Zn, and Mn adsorption at the root surface. Complexation of cations such as Cu, Pb, and Fe with high affinity for (dissolved) organic matter may lead to increased uptake of cations with low affinity for organic matter (Ni, Zn, and Cd) because of competition between cations at the root surface. The results suggest that competition between metal ions can play a major role in multicomponent metal uptake, which has to be taken into account during risk assessments of metal-polluted soils.

Metal uptake by Lolium perenne in contaminated soils using a four-step approach.

Most research dealing with soil (solution) speciation and metal uptake by plants has focused on the relationships between a certain bioavailable fraction in the soil and metal uptake by aboveground parts of the plants. Here, a new approach to interpretation of metal uptake is presented that considers four steps: First, the metal concentration in the soil solution is related to the total metal content of the soil. Second, the metal adsorption to the root surface is related to the metal concentration in the soil solution. Third, the metal content in the roots is related to the adsorption of metal ions to the root surface. Fourth, the metal content in the shoots is related to the metal content in the roots. For grass grown on 10 different soils, it is shown that the metal adsorption to the root surface is pH-dependently related to the free or total metal concentration in the soil solution. The metal content in the roots depends linearly on the metal adsorption at the root surface, whereas the metal content in the shoots depends on the metal content in the roots, either linearly (Zn) or reaching a maximum (Cu, Pb, and Cd). For the Ni content in the shoots as a function of the root content, the relation is pH dependent, probably because of the competition effects of Ca. The pH of the soil has to be taken into account when CaCl2 extractions are used as a basis for risk assessment toward plants.

Relationship between Metal Speciation in Soil Solution and Metal Adsorption at the Root Surface of Ryegrass

The total metal content of the soil or total metal concentration in the soil solution is not always a good indicator for metal availability to plants. Therefore, several speciation techniques have been developed that measure a defined fraction of the total metal concentration in the soil solution. In this study the Donnan Membrane Technique (DMT) was used to measure free metal ion concentrations in CaCl(2) extractions (to mimic the soil solution, and to work under standardized conditions) of 10 different soils, whereas diffusive gradients in thin-films (DGT) and scanning chronopotentiometry (SCP) were used to measure the sum of free and labile metal concentrations in the CaCl(2) extracts. The DGT device was also exposed directly to the (wetted) soil (soil-DGT). The metal concentrations measured with the speciation techniques are related to the metal adsorption at the root surface of ryegrass (Lolium perenne L.), to be able to subsequently predict metal uptake. In most cases the metal adsorption related pH-dependently to the metal concentrations measured by DMT, SCP, and DGT in the CaCl(2) extract. However, the relationship between metal adsorption at the root surface and the metal concentrations measured by the soil-DGT was not-or only slightly-pH dependent. The correlations between metal adsorption at the root surface and metal speciation detected by different speciation techniques allow discussion about rate limiting steps in biouptake and the contribution of metal complexes to metal bioavailability.

Impact of pH on CdII partitioning between alginate gel and aqueous media

Environmental context. Biogels, such as those in cell walls or biofilm matrices, generally comprise negative structural charge which leads to accumulation of positively charged species, e.g. metal ions. The magnitude of the effective charge, and hence the local chemical speciation within the gel phase, is pH dependent. In situ speciation measurements in biogels, such as the model alginate studied in this work, offer a better estimate of bioavailable concentrations than does analysis of the surrounding aqueous medium. Abstract. Many microorganisms exist in a biogel-mediated micro-environment such as a cell wall or a biofilm, in which local concentrations of ionic nutrients and pollutants differ from those in the surrounding bulk medium. The local concentration is the relevant parameter for considerations of bioavailability. These modified concentrations arise as a consequence of the negative charges within biogels which may induce a Donnan potential inside the biogel phase. For metals, the net effect on the speciation within the biogel, relative to the bulk medium, is an enhancement of the concentration of free cations. Since the structural charge in the biogel arises from protolytic functional groups, the Donnan potential is pH dependent. Here we apply in situ voltammetry to measure the free metal ion concentration inside alginate gel as a function of pH. In the pH range 3 to 7, the speciation of CdII within this model biogel can be explained by specific binding to carboxylic functional groups and electrostatic binding resulting from the Donnan potential.

Chapter 8 Process-based approach in the study of bioavailability of ions in soils

Publisher Summary This chapter discusses some recent studies and developments regarding the bioavailability issue. These studies include speciation measurement, speciation modeling, ion competition for uptake, and transport-controlled uptake. The general objective of these studies is to combine the measurement and modeling methods to develop mechanistic approaches to understand bioavailability of ions in terrestrial and aquatic systems. The bioavailability of an element can be expressed in terms of the concentration of the free ion and the concentration of other ions that are involved in the direct uptake. Because speciation influences the concentration of all species, it is likely to affect the concentration of the free ion and therefore the bioavailability is at least a function of the concentration of the free ion. The chapter discusses about strong correlations that are obtained between the free metal ion concentration and metal uptake for metal ions. An overview of Donnan membrane technique (DMT) is presented. Also, concepts related to speciation methods, DMT principle, and DMT setup are discussed. Multisurface models including speciation models and ion adsorption models are analyzed. A discussion on ion transport and bioavailability is presented. Competition between ions for uptake is also reviewed.