Zinc localization and speciation in rice grain under variable soil zinc deficiency

Background and aims Rice accounts for around 20% of the calories consumed by humans. Essential nutrients like zinc (Zn) are crucial for rice growth and for populations relying on rice as a staple food. No well-established study method exists. As a result, we a lack a clear picture of the chemical forms of zinc in rice grain. Furthermore, we do not understand the effects of widespread and variable zinc deficiency in soils on the Zn speciation, and to a lesser extent, its concentration, in grain. Methods The composition and Zn speciation of Cambodian rice grain is analyzed using synchrotron-based microprobe X-ray fluorescence (mu-XRF) and extended X-ray absorption fine-structure spectroscopy (EXAFS). We developed a method to quantify Zn species in different complexes based on the coordination numbers of Zn to oxygen and sulfur at characteristic bond lengths. Results Zn levels in brown rice grain ranged between 15-30 mg kg(-1) and were not correlated to Zn availability in soils. 72%-90% of Zn in rice grains is present as Zn-phytate, generally not bioavailable, while smaller quantities of Zn are bound as labile nicotianamine complexes, Zn minerals like ZnCO3 or thiols. Conclusion Zn speciation in rice grain is affected by Zn deficiency more than previously recognized. A majority of Zn was bound in phytate complexes in rice grain. Zinc phytate complexes were found in higher concentrations and also in higher proportions, in Zn-deficient soils, consistent with increased phytate production under Zn deficiency. Phytates are generally not bioavailable to humans, so low soil Zn fertility may not only impact grain yields, but also decrease the fraction of grain Zn bioavailable to human consumers. The potential impact of abundant Zn-phytate in environments deficient in Zn on human bioavailability and Zn deficiency requires additional research.