A pot experiment was conducted to study changes over time of Cd and Zn in soil solution and in plants. Radish was grown in a soil which had been contaminated with heavy metals prior to 1961. Constant amounts of a fertilizer solution (NH4N03, KN03) were added daily. Soil solution was obtained at intervals by displacement with water.The cumulative additions of small amounts of fertilizers were made equal to the plants' requirements at the final harvest but were found to exceed them during most of the experiment. Excess fertilizers caused substantial increases of major (K, Ca, Mg) and heavy-metal (Cd, Zn) ions in soil solutions and a decrease in soil pH, probably due to ion-exchange mechanisms and the dissolution of carbonates.Uptake of Cd and Zn into leaves was correlated with the mass flow of Cd (adjusted r2 = 0.798) and Zn (adjusted r2=0.859). Uptake of K, Ca and Mg by the plants was independent of their concentrations in solution.It is concluded that, in order to study effects of plants on heavy-metal availability and obtain soil solution that has not been altered by fertilizer ions, nutrients must be added according to the needs and growth of the plants. This could be achieved by linking fertilizer additions to the rate of transpiration, as nutrient uptake and transpiration were closely correlated in this experiment.

Soil solution was obtained from potted rhizosphere or non-rhizosphere soils by water displacement or soil centrifugation. The pH of the displaced solutions was lower than that of bulk soils when solutions were obtained from non-rhizosphere soil, although it increased as plants grew. This increase probably reflected true changes in rhizosphere pH, generated by the uptake by plants of N03-N. In contrast, the pH of soil centrifugates was usually close to that of the bulk soils, implying that buffering by colloids had occurred during sampling. Concentrations of elements in solutions from non-rhizosphere soil were similar for both methods when soils were incubated at ambient pCO2. However, when non-rhizosphere soils were incubated at elevated pC02, displacement solutions had lower pH values, and much larger concentrations of elements, compared to soil centrifugates.Comparison of mass flow of elements versus actual plant uptake showed that Ca and Mg accumulated, while K, Zn and Cd were depleted from the rhizosphere. Displacement solutions showed this accumulation or depletion of the elements more clearly than soil centrifugates. These differences were attributed to the fact that, at constant soil moisture, the rhizosphere developed mainly in larger pores, which were sampled by displacement. With centrifugation, a mixture of pore sizes was sampled, so that rhizosphere solution was only obtained when all of the soil had become rhizosphere.Soil centrifugates obtained after 22 days of growth also contained higher concentrations of organic carbon than displacement solutions, indicating contamination due to the disruption of roots and/or micro-organisms. We conclude that water displacement is suitable for sampling solution from light to medium textured rhizosphere or non-rhizosphere soils and that soil centrifugation is only of limited suitability.

Changes in the properties of soil solution in the rhizosphere of developing radish plants were investigated. Variations in these properties were expected to affect the distribution and speciation of metals in the soil and soil solution. Applications of essential nutrients were linked to plant transpiration rates and prevented excess addition of nutrient ions, so that subtle changes in soil solution composition would not be obscured. Soil solution pH, the concentration of dissolved organic carbon (DOC) and the concentrations of major and trace elements in solution were found to vary over time. Strict control of fertilizer additions led to the maintenance of a relatively low ionic strength in the soil solution, and under such conditions trace metal solubility appeared to be highy influenced by the concentration of DOC. A chemical speciation analysis was performed which showed that, while dissolved Cd and Zn were largely uncomplexed in unplanted soil, Cd and Zn in the rhizosphere existed mainly as complexed forms. It is hypothesized that this is partly a result of Ca‐metal‐ligand equilibrium in solution, with higher Ca concentrations in unplanted soil leading to more of the Cd and Zn in solution existing in the uncomplexed state. Changes in the concentrations of uncomplexed Cd and Zn with time gave the best correlations with changes in plant uptake of these metals over time, supporting the hypothesis that plants mainly absorb the free metal ion from soil solution.

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