Chemical Speciation of Heavy Metals in the Fractionated Rhizosphere Soils of Sunflower Cultivated in a Humic Andosol

Chemical speciation and bioaccumulation factor of iron (Fe), manganese (Mn), and zinc (Zn) were investigated in the fractionated rhizosphere soils and tissues of sunflower plants grown in a humic Andosol. The experiment was conducted for a period of 35 days in the greenhouse, and at harvest the soil system was differentiated into bulk, rhizosphere, and rhizoplane soils based on the collection of root-attaching soil aggregates. The chemical speciations of heavy metals in the soil samples were determined after extraction sequentially into fractions classified as exchangeable, carbonate bound, metal-organic complex bound, easily reducible metal oxide bound, hydrogen peroxide (H2O2)-extractable organically bound, amorphous mineral colloid bound, and crystalline Fe oxide bound. Iron and Zn were predominantly crystalline Fe oxide bound in the initial bulk soils whereas Mn was mainly organically bound. Heavy metals in the exchangeable form accumulated in the rhizosphere and rhizoplane soils, comprising <4% of the total content, suggesting their relatively low availability in humic Andosol. Concentrations of organically bound Fe and Mn in soils decreased with the proximity to roots, suggesting that organic fraction is the main source for plant uptake. Concentrations of Mn and Zn in the metal-organic complex also decreased, indicating a greater ability of sunflower to access Mn from more soil pools. Sunflower showed bioaccumulation factors for Zn, Fe, and Mn as large as 0.39, 0.05, and 0.04 respectively, defining the plant as a metal excluder species. This result suggests that access to multiple metal pools in soil is not necessarily a major factor that governs metal accumulation in the plant.