Abstract Micronutrient deficiencies threaten global food production. Attempts to biofortify crops rely on a clear understanding of micronutrient uptake processes. Zinc deficiency in rice is a serious problem. One of the pathways proposed for the transfer of zinc from soils into rice plants involves deoxymugineic acid (DMA), a phytosiderophore. The idea that phytosiderophores play a wider role in nutrition of Poaceae beyond iron is well established. However, key mechanistic details of the DMA-assisted zinc uptake pathway in rice remain uncertain. In particular, questions surround the form in which zinc from DMA is taken up [i.e. as free aqueous Zn(II) or as Zn(II)–DMA complexes] and the role of competitive behaviour of other metals with DMA. We propose that an accurate description of the effect of changes in pH, ligand concentration, and ionic strength on the stability of Zn(II)–DMA complexes in the presence of other metals in the microenvironment around root cells is critical for understanding the modus operandi of DMA during zinc uptake. To that end, we reveal the importance of geochemical changes in the microenvironment around root cells and demonstrate the effect of inaccurate stability constants on speciation models.