No abstract

Zinc deficiencies are generally more widespread on calcareous soils than are Cu deficiencies. The concentration and the degree of complexing of Zn and Cu were measured in the soil solution of 20 calcareous soils from Colorado. The Zn levels in solution were generally less than 2 ppb with rarely more than 75% of the Zn being complexed. Copper levels generally ranged from 5 to 16 ppb in the soil solution with 98 to 99% of the Cu present as organic complexes. Thus, complexing increased the total Cu concentration in solution by a factor of about 100, whereas it increased the total Zn in solution by a factor of 4 or less. Compared to acid soils studied previously, soluble Zn levels were much lower and complexing of Cu was somewhat higher in calcareous soils.

Procedures were developed for the partition of heavy metals (Cu, Co, and Zn) between complexed and uncomplexed forms in soil solution. Competition for the above cations by complexing agents naturally present in soil solution and added complexing agents that form metal complexes soluble in organic solvents was determined by measuring the distribution of metal between aqueous and organic phases in a two-phase system. The degree to which the metal was complexed in the original soil solution could be deduced by comparing the amount of metal extracted from soil solution with that extracted from water at the same pH. Examination of soil solutions from several mineral soils indicated that in the case of Cu as much as 99% of the metal may exist in a complexed form.

Specific reactions between montmorillonite and Co in low concentrations were studied in the presence of excess CaCl2. Two forms of bound Co were distinguished. One form, characterized as being slowly dissociable, appears to be bound in a monolayer by chemisorption and will exchange with Cu++, Zn++, or other Co++ and to a lesser extent with ions of other transition metals but not with Ca++, Mg++, or NH4+. A second form of Co did not dissociate and could not be extracted from the mineral with 2.5% acetic acid. This fraction, which was not characterized, is thought to either enter the crystal lattice or be occluded in the precipitation of another phase.

At least three groups of compounds were found to complex Zn2+ and Cu2+ in soil solution from the A horizon of a Williamson silt loam. A nondialyzable fraction of soil solution ligands had a poorly defined acid dissociation, pKa, ranging from 3 to 4.7. The dialyzable fraction had acid dissociation constants of 4.5 and 9.5, which were attributed to aliphatic and amino acids, respectively. The equivalent concentration of the nondialyzable acid fraction was only 1/40 that of the dialyzable fraction, but was more effective in complexing Zn and Cu in the soil solution. The average metal/ligand ratio was equal to unity in complexes of both the dialyzable and nondialyzable fractions with Zn2+ and Cu2+. Estimated, log10 (average formation constants) of the nondialyzable‐metal complexes were calculated on the basis of titratable acidity as 4.3 ± 0.1 and 5.5 ± 0.1 for Zn2+ and Cu2+, respectively.