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Total concentrations of metals in soil are poor predictors of toxicity. In the last decade, considerable effort has been made to demonstrate how metal toxicity is affected by the abiotic properties of soil. Here this information is collated and shows how these data have been used in the European Union for defining predicted-no-effect concentrations (PNECs) of Cd, Cu, Co, Ni, Pb, and Zn in soil. Bioavailability models have been calibrated using data from more than 500 new chronic toxicity tests in soils amended with soluble metal salts, in experimentally aged soils, and in field-contaminated soils. In general, soil pH was a good predictor of metal solubility but a poor predictor of metal toxicity across soils. Toxicity thresholds based on the free metal ion activity were generally more variable than those expressed on total soil metal, which can be explained, but not predicted, using the concept of the biotic ligand model. The toxicity thresholds based on total soil metal concentrations rise almost proportionally to the effective cation exchange capacity of soil. Total soil metal concentrations yielding 10% inhibition in freshly amended soils were up to 100-fold smaller (median 3.4-fold, n = 110 comparative tests) than those in corresponding aged soils or field-contaminated soils. The change in isotopically exchangeable metal in soil proved to be a conservative estimate of the change in toxicity upon aging. The PNEC values for specific soil types were calculated using this information. The corrections for aging and for modifying effects of soil properties in metal-salt-amended soils are shown to be the main factors by which PNEC values rise above the natural background range.

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Uptake of Cd and Zn by intact seedlings of two contrasting ecotypes of the hyperaccumulator Thlaspi caerulescens was characterized using radioactive tracers. Uptake of Cd and Zn at 2 degrees C was assumed to represent mainly apoplastic binding in the roots, whereas the difference in uptake between 22 degrees C and 2 degrees C represented metabolically dependent influx. There was no significant difference between the two ecotypes in the apoplastic binding of Cd or Zn. Metabolically dependent uptake of Cd was 4.5-fold higher in the high Cd-accumulating ecotype, Ganges, than in the low Cd-accumulating ecotype, Prayon. By contrast, there was only a 1.5-fold difference in the Zn uptake between the two ecotypes. For the Ganges ecotype, Cd uptake could be described by Michaelis-Menten kinetics with a V(max) of 143 nmol g(-1) root FW h(-1) and a K(m) of 0.45 microM. Uptake of Cd by the Ganges ecotype was not inhibited by La, Zn, Cu, Co, Mn, Ni or Fe(II), and neither by increasing the Ca concentration. By contrast, addition of La, Zn or Mn, or increasing the Ca concentration in the uptake solution decreased Cd uptake by Prayon. Uptake of Ca was larger in Prayon than in Ganges. The results suggest that Cd uptake by the low Cd-accumulating ecotype (Prayon) may be mediated partly via Ca channels or transporters for Zn and Mn. By contrast, there may exist a highly selective Cd transport system in the root cell membranes of the high Cd-accumulating ecotype (Ganges) of T. caerulescens.

Metal pollution of agricultural land in Australia and New Zealand is less severe than that documented in many European countries, due to the lower density of urban developments and a lower level of industrialisation. However, Australia and New Zealand are highly dependent on plant production systems based on plant-microbial symbioses (e.g. Rhizobium, mycorrhizae) and other natural biogeochemical processes for maintaining nutrient status in soils that are generally low in nutrients and, in Australia, also low in organic matter. Data linking metal concentrations in soil to agricultural and ecological effects are sparse for Australia and New Zealand, and regulatory frameworks and guidelines to control metal contamination of soils rely heavily on data generated in countries of the northern hemisphere. Adoption of benchmark concentrations for metal contaminants from these countries has led to inappropriate levels being chosen for several elements. These problems could be avoided and metal contamination of soils could be more effectively controlled if instead of relying on total concentrations of metals in soil and soil amendments, regulations and guidelines considered the biologically active fractions. This review considers the advantages and disadvantages of a bioavailability-based approach to the control of metal contamination of soils and suggests improvements needed to avoid both over- and under-protective measures.

To predict the availability of metals to plants, it is important to understand both solution- and solid-phase processes in the soil, including the kinetics of metal release from its binding agent (ligand and/or particle). The present study examined the speciation and availability of Zn, Cd, Pb, and Cu in a range of well-equilibrated metal-contaminated soils from diverse sources using several techniques as a basis for predicting metal uptake by plants. Wheat (Triticum aestivum L.) was grown in 13 metal-contaminated soils and metal tissue concentrations (Zn, Cd, Pb, and Cu) in plant shoots were compared with total soil metal concentrations, total soluble metal, and free metal activities (pM2+) in soil pore waters, 0.01 M CaCl2-extractable metal concentrations, E values measured by isotope dilution, and effective metal concentrations, C(E), measured by diffusive gradients in thin films (DGT). In the DGT technique, ions are dynamically removed by their diffusion through a gel to a binding resin, while E values represent the isotopically exchangeable (labile) metal pools. Free metal activities (Zn2+, Cd2+, and Pb2+) in soil pore waters were determined using a Donnan dialysis technique. Plant Zn and Cd concentrations were highly related to C(E), while relationships for Zn and Cd with respect to the other measures of metals in the soils were generally lower, except for CaCl2-extractable Cd. These results suggest that the kinetically labile solid-phase pool of metal, which is included in the DGT measurement, played an important role in Zn and Cd uptake by wheat along with the labile metal in soil solution. Plant Pb concentrations were highly related to both soil pore water concentrations and C(E), indicating that supply from the solid phase may not be so important for Pb. Predictions of Cu uptake by wheat from these soils by the various measures of Cu were generally poor, except surprisingly for total Cu.

The effects of soil properties and zinc (Zn) availability on the toxicity of Zn to soil microbial processes are poorly understood. Three soil microbial processes--potential nitrification rate (PNR), substrate (glucose)-induced respiration (SIR), and a maize residue respiration (MRR)--were measured in 15 European topsoils (pH 3.0-7.5; total Zn 7-191 mg/kg) that were freshly spiked with ZnCl2. The Zn toxicity thresholds of 20 to 50% effective concentrations (EC20s and EC50s) based on total concentrations of Zn in soil varied between 5- and 26-fold among soils, depending on the assay. The Zn toxicity thresholds based on Zn concentrations in soil solution varied at least 10-fold more than corresponding total metal thresholds. Soil pH had no significant effect on soil total Zn toxicity thresholds, whereas significant positive correlations were found between these thresholds and background Zn for the PNR and SIR test (r = 0.74 and 0.71, respectively; log-log correlations). No such trend was found for the MRR test. Soil solution-based thresholds showed highly significant negative correlations with soil pH for all assays that might be explained by competition of H+ for binding sites, as demonstrated for aquatic species. The microbial assays were also applied to soils collected under galvanized pylons (three sites) where concentrations of total Zn were up to 2,100 to 3,700 mg Zn/kg. Correlations between concentrations of total Zn and microbial responses were insignificant at all sites even though spiking reference samples to equivalent concentrations reduced microbial activities up to more than 10-fold. Differences in response between spiked and field soils are partly but not completely attributed to the large differences in concentrations of Zn in soil solution. We conclude that soil pH has no significant effect on Zn toxicity to soil microbial processes in laboratory-spiked soils, and we suggest that community tolerance takes place at both background and elevated Zn concentrations in soil.

Natural attenuation of metals added to soils refers to the processes by which the mobility and bioavailability/toxicity of the added metals decline with time. In this paper, we used isotopic dilution techniques to investigate the short-term (30 d) natural attenuation of Cu added to 19 European soils at two effective concentrations shown to inhibit plant (tomato) growth by 10 and 90%. The results showed that the lability of Cu added to soils rapidly decreased after addition, especially in the soils with pH > 6.0, followed by a slow decrease in Cu lability. The lability of Cu added to soils also decreased with increasing incubation temperature. The activation energies and the apparent diffusion rate coefficients for the attenuation processes were 33 to 36 kJ/mol and 0.66 to 20.9 x 10(-10)/s at 20 degrees C, respectively, and were consistent with Cu diffusion in meso- and micropores. The attenuation of Cu lability was modeled on the basis of three processes: precipitation/nucleation of Cu on soil surfaces, Cu occlusion within organic matter, and diffusion of Cu into micropores. The soil and environmental factors governing attenuation rates were soil pH, organic matter content, incubation time, and temperature. Soil pH is the key factor for natural attenuation of Cu added to soils. The model can be used to scale ecotoxicological data generated from different soils and under different incubation times and temperatures.