Both experimental extractions and theoretical calculations were undertaken to assess whether organic acid-mediated Fe dissolution could play a significant role in elevating the concentration of Fe-complexes in the rhizosphere, and further, whether this could satisfy the Fe demands of a plant utilizing ferric reduction to acquire Fe. Using a mathematical computer model, it was predicted that organic acids released from and diffusing away from the root would result in a solution organic acid concentration at the root surface of between 1 to 50 μM. Over 99% of the organic acids lost by the root were predicted to remain within 1 mm of the root surface. The experimental results indicated that citrate-mediated Fe dissolution of amorphous Fe(OH)3, was rapid in comparison with citrate dissolution of the Fe-oxides, Fe2O3 and Fe3O4. The rate of citrate and malate mediated Fe- dissolution was dependent on many factors such as pH, metal cations and phosphate saturation of the Fe(OH)3 surface. At pH values ≤6.8, citrate formed stable complexes with Fe and dissolution proceeded rapidly. Under optimal growth conditions for a plant utilizing a reductive-bound mechanism of Fe acquisition (dicots and non-grass monocots), it can be expected that citrate and malate may be able to satisfy a significant proportion of the plant's Fe demand through the formation of plant-available organic-Fe3+ complexes in the rhizosphere. In high pH soils (pH ≤7.0), the plant must rely on other sources of Fe, as citrate-mediated Fe dissolution is slow and Fe-citrate complexes are unstable. Alternatively, the root acidification of the rhizosphere could allow the formation of stable Fe-organic complexes.