Reevaluating the free-ion activity model of trace metal toxicity toward higher plants: experimental evidence with copper and zinc.
Across a diverse spectrum of organisms, the absorption and toxicity of trace elements are usually correlated with the activity of the free metal ion, but reported exceptions to this generalization are increasing. For the first time, we tested the validity of the free-ion activity model (FIAM) in the case of terrestrial plants and organic acids that may be abundant in the soil solution and rhizosphere. Short-term (48-h) root elongation of wheat (Triticum aestitvum L.) in a simple medium (2 mM CaCl2, pH 6.0) was used to probe the toxicity of Cu and Zn in the presence of malonate, malate, and citrate. Precautions were taken to prevent biodegradation of the organic acids, and its absence was confirmed by ion chromatography. Copper speciation was verified using a Cu-selective ion electrode, and published stability constants were modified to improve agreement between measured and calculated Cu2+ activities. With additions of both malonate and malate, Cu toxicity was alleviated but not to the extent predicted by the FIAM; the Cu-ligand complexes seemingly contributed to the toxicity. No such departures were observed with citrate and Cu nor with any of the three ligands in combination with Zn. Thus, exceptions to the FIAM occur with higher plants as well as with aquatic biota but do not seem to occur in a predictable or systematic fashion with respect to metal or organic acid under investigation. Several possible explanations for the observed departures from the FIAM are discussed, including the possibility of accidental cotransport of metal and ligand into the cytoplasm.